Metal oxide semiconductor-based light emitting device

ABSTRACT

An optoelectronic semiconductor light emitting device configured to emit light having a wavelength in the range from about 150 nm to about 425 nm is disclosed. In embodiments, the device comprises a substrate having at least one epitaxial semiconductor layer disposed thereon, wherein each of the one or more epitaxial semiconductor layers comprises a metal oxide. An epitaxial semiconductor layer of the device can include a first single crystal oxide material. The first single crystal oxide material can include: at least one of magnesium, nickel, and zinc; at least one of aluminum and gallium; and oxygen. The first single crystal oxide material can also include a cubic crystal symmetry.

RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/990,349 filed on Aug. 11, 2020 and entitled “Metal OxideSemiconductor-Based Light Emitting Device,” which claims priority toAustralian Provisional Patent Application No. 2020901513, filed on May11, 2020 and entitled “Metal Oxide Semiconductor Based Light EmittingDevice”; the contents of which are hereby incorporated by reference intheir entirety.

The following publications are referred to in the present applicationand their contents are hereby incorporated by reference in theirentirety:

-   U.S. Pat. No. 9,412,911 titled “OPTICAL TUNING OF LIGHT EMITTING    SEMICONDUCTOR JUNCTIONS”, issued 9 Aug. 2016, and assigned to the    applicant of the present application;-   U.S. Pat. No. 9,691,938 titled “ADVANCED ELECTRONIC DEVICE    STRUCTURES USING SEMICONDUCTOR STRUCTURES AND SUPERLATTICES”, issued    27 Jun. 2017, and assigned to the applicant of the present    application;-   U.S. Pat. No. 10,475,956 titled “OPTOELECTRONIC DEVICE”, issued 12    Nov. 2019, and assigned to the applicant of the present application;    and

The contents of each of the above publications are expresslyincorporated by reference in their entirety.

BACKGROUND

Ultraviolet light emitting devices (UVLEDs) have many applications inmedicine, medical diagnostics, water purification, food processing,sterilization, aseptic packaging and deep submicron lithographicprocessing. Emerging applications in bio-sensing, communications,pharmaceutical process industry and materials manufacturing are alsoenabled by delivering extremely short wavelength optical sources in acompact and lightweight package having high electrical conversionefficiency such as a UVLED.

Electro-optical conversion of electrical energy into discrete opticalwavelengths with extremely high efficiency has generally been achievedusing a tailor-made semiconductor having the required properties toachieve the spatial recombination of charge carriers of electrons andholes to emit light of the required wavelength. In the case where UVlight is required, UVLEDs have been developed using almost exclusivelyGallium-Indium-Aluminum-Nitride (GaInAlN) compositions formingwurtzite-type crystal structures.

Group-III-Nitrides have been used in semiconductor based UVLEDs thatgenerate light in the UVC wavelength band (i.e., wavelength betweenapproximately 200 nm to 280 nm) fundamentally based on heterojunctionp-i-n diodes. Unfortunately, the efficiency and output optical power inthe UVC region appears to be limited by the inherent lowcrystallographic structure quality of the AlInGaN epitaxially depositedlayers fundamentally due to the lack of native substrates, such as AlN.

Sapphire (corundum Al₂O₃) has been suggested as a compromise startingsurface crystal to heterogeneously seed two very different materialssystems. However, there is a large structural mismatch between thesapphire crystal and the Group-III-Nitrides. The crystal lattice andsymmetry mismatch creates a very large density of disadvantageouscrystalline defects which detracts severely from the ultimate efficiencyof Group-III-Nitride based UVLEDs. Even if this defect density could bereduced by several orders in magnitude, the highest bandgap material AlNlimits UVC operation to approximately 215 nm, with a dramatic decline inoutput optical power as the wavelength is reduced below 280 nm.

SUMMARY

In some embodiments, an optoelectronic semiconductor light emittingdevice includes a substrate and a plurality of epitaxial semiconductorlayers disposed on the substrate. Each of the epitaxial semiconductorlayers comprises a metal oxide. The optoelectronic semiconductor lightemitting device is configured to emit light having a wavelength in arange from 150 nm to 425 nm.

In some embodiments, an optoelectronic semiconductor device forgenerating light of a predetermined wavelength includes a substrate andan optical emission region. The optical emission region has an opticalemission region band structure configured for generating light of thepredetermined wavelength. The optical emission region has an epitaxialmetal oxide layer supported by the substrate, where the epitaxial metaloxide layer has an optical emission region band gap energy capable ofgenerating light of the predetermined wavelength.

In some embodiments, an optoelectronic semiconductor light emittingdevice includes a substrate and a plurality of epitaxial semiconductorlayers disposed on the substrate. A first epitaxial semiconductor layerof the epitaxial semiconductor layers can include a first single crystaloxide material. The first single crystal oxide material can include: atleast one of magnesium, nickel, and zinc; at least one of aluminum andgallium; and oxygen. The first single crystal oxide material can includea cubic crystal symmetry. The optoelectronic semiconductor lightemitting device can be configured to emit light having a wavelength in arange from 150 nm to 425 nm.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the present disclosure will be discussed with referenceto the accompanying figures wherein:

FIG. 1 is process flow diagram for constructing a metal oxidesemiconductor-based LED in accordance with an illustrative embodiment ofthe present disclosure;

FIGS. 2A and 2B depict schematically two classes of LED devices based onvertical and waveguide optical confinement and emission disposed upon asubstrate in accordance with illustrative embodiments of the presentdisclosure;

FIGS. 3A-3E are schematic diagrams of different LED deviceconfigurations in accordance with illustrative embodiments of thepresent disclosure comprising a plurality of regions;

FIG. 4 depicts schematically the injection of oppositely chargedcarriers from physically separated regions into a recombination regionin accordance with an illustrative embodiment of the present disclosure;

FIG. 5 shows the optical emission directions possible from the emissionregion of an LED in accordance with an illustrative embodiment of thepresent disclosure;

FIG. 6 depicts an aperture through an opaque region to enable lightemission from an LED in accordance with an illustrative embodiment ofthe present disclosure;

FIG. 7 shows example selection criteria to construct a metal oxidesemiconductor structure in accordance with an illustrative embodiment ofthe present disclosure;

FIG. 8 is an example process flow diagram for selecting and depositingepitaxially a metal oxide structure in accordance with an illustrativeembodiment of the present disclosure;

FIG. 9 is a summary of technologically relevant semiconductor bandgapsas a function of electron affinity, showing relative band lineups;

FIG. 10 is an example schematic process flow for depositing a pluralityof layers for forming a plurality of regions comprising an LED inaccordance with an illustrative embodiment of the present disclosure;

FIG. 11 is a ternary alloy optical bandgap tuning curve for metal oxidesemiconductor ternary compositions based on Gallium-Oxide in accordancewith illustrative embodiments of the present disclosure;

FIG. 12 is a ternary alloy optical bandgap tuning curve for metal oxidesemiconductor ternary compositions based on Aluminum-Oxide in accordancewith illustrative embodiments of the present disclosure;

FIGS. 13A and 13B are electron energy-vs.-crystal momentumrepresentations of metal oxide based optoelectronic semiconductorsshowing a direct bandgap (FIG. 13A) and indirect bandgap (FIG. 13B) inaccordance with illustrative embodiments of the present disclosure;

FIGS. 13C-13E are electron energy-vs.-crystal momentum representationsshowing allowed optical emission and absorption transitions at k=0 withrespect to the axes of Ga₂O₃ monoclinic crystal symmetry in accordancewith an illustrative embodiment of the present disclosure;

FIGS. 14A and 14B depict sequential deposition of a plurality ofheterogenous metal oxide semiconductor layers having dissimilar crystalsymmetry types to embed an optical emission region in accordance with anillustrative embodiment of the present disclosure;

FIG. 15 is a schematic representation of an atomic deposition tool forthe creation of multi-layered metal oxide semiconductor films comprisinga plurality of material compositions in accordance with illustrativeembodiments of the present disclosure;

FIG. 16 is a representation of sequential deposition of layers andregions having similar crystal symmetry types matching the substrate inaccordance with an illustrative embodiment of the present disclosure;

FIG. 17 depicts sequential deposition of regions having a differentcrystal symmetry to an underlying first surface of a substrate where asurface modification to the substrate is shown in accordance with anillustrative embodiment of the present disclosure;

FIG. 18 depicts a buffer layer deposited with the same crystal symmetryas an underlying substrate to enable subsequent hetero-symmetrydeposition of oxide materials in accordance with an illustrativeembodiment of the present disclosure;

FIG. 19 depicts a structure comprising a plurality of hetero-symmetricalregions sequentially deposited as a function of the growth direction inaccordance with an illustrative embodiment of the present disclosure;

FIG. 20A shows a crystal symmetry transition region linking twodeposited crystal symmetry types in accordance with an illustrativeembodiment of the present disclosure;

FIG. 20B shows the variation in a particular crystal surface energy as afunction of crystal surface orientation for the cases ofcorundum-Sapphire and monoclinic Gallia single crystal oxide materialsin accordance with an illustrative embodiment of the present disclosure;

FIGS. 21A-21C depict schematically the change in electronic energyconfiguration or band structure of a metal oxide semiconductor under theinfluence of bi-axial strain applied to the crystal unit cell inaccordance with an illustrative embodiment of the present disclosure;

FIGS. 22A and 22B depict schematically the change in band structure of ametal oxide semiconductor under the influence of uniaxial strain appliedto the crystal unit cell in accordance with an illustrative embodimentof the present disclosure;

FIGS. 23A-23C show the effect on the band structure of monoclinicgallium-oxide as a function of applied uniaxial strain to the crystalunit cell in accordance with an illustrative embodiment of the presentdisclosure;

FIGS. 24A and 24B depict the E-k electronic configuration of twodissimilar binary metal oxides in accordance with an illustrativeembodiment of the present disclosure: one having a wide direct-bandgapmaterial and the other a narrow indirect-bandgap material;

FIGS. 25A-25C show the effect of valence band mixing of two binarydissimilar metal oxide materials that together form a ternary metaloxide alloy in accordance with an illustrative embodiment of the presentdisclosure;

FIG. 26 depicts schematically a portion of the energy-vs-crystalmomentum of dominant valence bands sourced from two bulk-like metaloxide semiconductor materials up to the first Brillouin zone inaccordance with an illustrative embodiment of the present disclosure;

FIGS. 27A-27B show an effect of a superlattice (SL) in one dimension onthe E-k configuration for a layered structure having a superlatticeperiod equal to approximately twice the bulk lattice constant of thehost metal oxide semiconductors, depicting the creation of asuperlattice Brillouin-zone that opens an artificial bandgap at a zonecenter in accordance with an illustrative embodiment of the presentdisclosure;

FIG. 27C shows a bi-layered binary superlattice comprising a pluralityof thin epitaxial layers of Al₂O₃ and Ga₂O₃ repeating with a fixed unitcell period where the digital alloy simulates an equivalent ternaryAl_(x)Ga_(1−x)O₃ bulk alloy depending on the constituent layer thicknessratio of the superlattice period in accordance with an illustrativeembodiment of the present disclosure;

FIG. 27D shows another bi-layered binary superlattice comprising aplurality of thin epitaxial layers of NiO and Ga₂O₃ repeating with afixed unit cell period where the digital alloy simulates an equivalentternary (NiO)_(x)(Ga₂O₃)_(1−x) bulk alloy depending on the constituentlayer thickness ratio of the superlattice period in accordance with anillustrative embodiment of the present disclosure;

FIG. 27E shows yet another triple material binary superlatticecomprising a plurality of thin epitaxial layers of MgO, NiO repeatingwith a fixed unit cell period where the digital alloy simulates anequivalent ternary bulk alloy (NiO)_(x)(MgO)_(1−x) depending on theconstituent layer thickness ratio of the superlattice period and wherethe binary metal oxides used for the repeating unit are each selected tovary from between 1 to 10 unit cells in thickness respectively totogether comprise the unit cell of the SL in accordance with anillustrative embodiment of the present disclosure.

FIG. 27F shows yet another possible four-material binary superlatticecomprising plurality of thin epitaxial layers of MgO, NiO and Ga₂O₃repeating with a fixed unit cell period where the digital alloysimulates an equivalent quaternary bulk alloy(NiO)_(x)(Ga₂O₃)_(y)(MgO)_(z) depending on the constituent layerthickness ratio of the superlattice period where the binary metal oxidesused for the repeating unit are each selected to vary from between 1 to10 unit cells in thickness respectively to comprise the unit cell of theSL in accordance with an illustrative embodiment of the presentdisclosure;

FIG. 28 shows a chart of ternary metal oxide combinations that may beadopted in accordance with various illustrative embodiments of thepresent disclosure in the forming of optoelectronic devices;

FIG. 29 is an example design flow diagram for tuning and constructingoptoelectronic functionality of LED regions in accordance with anillustrative embodiment of the present disclosure;

FIG. 30 shows a heterojunction band lineup for the binary Al₂O₃, ternaryalloy (Al,Ga)O₃ and binary Ga₂O₃ semiconducting oxides in accordancewith an illustrative embodiment of the present disclosure;

FIG. 31 shows a 3-dimensional crystal unit cell of corundum symmetrycrystal structure (alpha-phase) Al₂O₃ used to calculate the E-k bandstructure in accordance with an illustrative embodiment of the presentdisclosure;

FIGS. 32A and 32B show a calculated energy-momentum configuration ofalpha-Al₂O₃ in the vicinity of the Brillouin zone center in accordancewith an illustrative embodiment of the present disclosure;

FIG. 33 shows a 3-dimensional crystal unit cell of a monoclinic symmetrycrystal structure Al₂O₃ used to calculate the E-k band structure inaccordance with an illustrative embodiment of the present disclosure;

FIGS. 34A and 34B show calculated energy-momentum configurations oftheta-Al₂O₃ in the vicinity of the Brillouin zone center in accordancewith an illustrative embodiment of the present disclosure;

FIG. 35 shows a 3-dimensional crystal unit cell of a corundum symmetrycrystal structure (alpha-phase) Ga₂O₃ used to calculate the E-k bandstructure in accordance with an illustrative embodiment of the presentdisclosure;

FIGS. 36A and 36B show calculated energy-momentum configurations ofcorundum alpha-Ga₂O₃ in the vicinity of the Brillouin zone center inaccordance with an illustrative embodiment of the present disclosure;

FIG. 37 shows a 3-dimensional crystal unit cell of a monoclinic symmetrycrystal structure (beta-phase) Ga₂O₃ used to calculate the E-k bandstructure in accordance with an illustrative embodiment of the presentdisclosure;

FIGS. 38A and 38B show calculated energy-momentum configurations ofbeta-Ga₂O₃ in the vicinity of the Brillouin zone center in accordancewith an illustrative embodiment of the present disclosure;

FIG. 39 shows a 3-dimensional crystal unit cell of an orthorhombicsymmetry crystal structure of bulk ternary alloy of (Al, Ga)O₃ used tocalculate the E-k band structure in accordance with an illustrativeembodiment of the present disclosure;

FIG. 40 shows a calculated energy-momentum configuration of (Al, Ga)O₃in the vicinity of the Brillouin zone center showing a direct bandgap inaccordance with an illustrative embodiment of the present disclosure;

FIG. 41 is a process flow diagram for forming an optoelectronicsemiconductor device in accordance with an illustrative embodiment ofthe present disclosure;

FIG. 42 depicts a cross-sectional portion of a (Al,Ga)O₃ ternarystructure formed by sequentially depositing Al—O—Ga—O— . . . —O—Alepilayers along a growth direction in accordance with an illustrativeembodiment of the present disclosure;

FIG. 43A shows in TABLE I a selection of substrate crystals fordepositing metal oxide structures in accordance with variousillustrative embodiments of the present disclosure;

FIG. 43B shows in TABLE II unit cell parameters of a selection of metaloxides in accordance with various illustrative embodiments of thepresent disclosure, showing lattice constant mismatches between Al₂O₃and Ga₂O₃;

FIG. 44A depicts a calculated formation energy of Aluminum-Gallium-Oxideternary alloy as a function of composition and crystal symmetry inaccordance with an illustrative embodiment of the present disclosure;

FIG. 44B shows an experimental high-resolution x-ray diffraction (HRXRD)of two example distinct compositions of high-quality single crystalternary (Al_(x)Ga_(1−x))₂O₃ deposited epitaxially on a bulk(010)-oriented Ga₂O₃ substrate in accordance with an illustrativeembodiment of the present disclosure;

FIG. 44C shows an experimental HRXRD and x-ray grazing incidencereflection (GIXR) of an example superlattice comprising repeating unitcells of bilayers selected from a [(Al_(x)Ga_(1−x))₂O₃/Ga₂O₃]elastically strained to a β-Ga₂O₃(010)-oriented substrate in accordancewith an illustrative embodiment of the present disclosure;

FIG. 44D shows an experimental HRXRD and GIXR of two example distinctcompositions of high-quality single crystal ternary (Al_(x)Ga_(1−x))₂O₃layers deposited epitaxially on a bulk (001)-oriented Ga₂O₃ substrate inaccordance with an illustrative embodiment of the present disclosure;

FIG. 44E shows an experimental HRXRD and GIXR of a superlatticecomprising repeating unit cells of bilayers selected from a[(Al_(x)Ga_(1−x))₂O₃/Ga₂O₃] elastically strained to aβ-Ga₂O₃(001)-oriented substrate in accordance with an illustrativeembodiment of the present disclosure;

FIG. 44F shows an experimental HRXRD and GIXR of a cubic crystalsymmetry binary Nickel Oxide (NiO) epilayer elastically strained to amonoclinic crystal symmetry β-Ga₂O₃(001)-oriented substrate inaccordance with an illustrative embodiment of the present disclosure;

FIG. 44G shows an experimental HRXRD and GIXR of a monoclinic crystalsymmetry Ga₂O₃(100)-oriented epilayer elastically strained to a cubiccrystal symmetry MgO(100)-oriented substrate in accordance with anillustrative embodiment of the present disclosure;

FIG. 44H shows an experimental HRXRD and GIXR of a superlatticecomprising repeating unit cells of bilayers selected from a[(Al_(x)Er_(1−x))₂O₃/Al₂O₃] elastically strained to a corundum crystalsymmetry α-Al₂O₃(001)-oriented substrate in accordance with anillustrative embodiment of the present disclosure;

FIG. 44I shows a strain-free energy-crystal momentum (E-k) dispersion inthe vicinity of the Brillouin-zone center for the case of a ternaryAluminum-Erbium-Oxide (Al_(x)Er_(1−x))₂O₃ illustrating the directbandgap at Γ(k=0) in accordance with an illustrative embodiment of thepresent disclosure;

FIG. 44J shows an experimental HRXRD and GIXR of a superlatticecomprising bilayered unit cells of a monoclinic crystal symmetryGa₂O₃(100)-oriented film coupled to a cubic (spinel) crystal symmetryternary composition of Magnesium-Gallium-Oxide,Mg_(x)Ga_(2(1−x))O_(3−2x) where the SL is epitaxially deposited upon amonoclinic Ga₂O₃(010)-oriented substrate in accordance with anillustrative embodiment of the present disclosure;

FIG. 44K shows a strain-free energy-crystal momentum (E-k) dispersion inthe vicinity of the Brillouin-zone center for the case of ternaryMagnesium-Gallium-Oxide Mg_(x)Ga_(2(1−x))O_(3−2x) illustrating thedirect bandgap at Γ(k=0) in accordance with an illustrative embodimentof the present disclosure;

FIG. 44L shows an experimental HRXRD and GIXR of an orthorhombic Ga₂O₃epilayer elastically strained to a cubic crystal symmetryMagnesium-Aluminum-Oxide MgAl₂O₄(100)-oriented substrate in accordancewith an illustrative embodiment of the present disclosure;

FIG. 44M shows an experimental HRXRD of a ternary Zinc-Gallium-OxideZnGa₂O₄ epilayer elastically strained to a wurtzite Zinc-Oxide ZnO layerdeposited upon a monoclinic crystal symmetry Gallium-Oxide(−201)-oriented substrate in accordance with an illustrative embodimentof the present disclosure;

FIG. 44N shows an energy-crystal momentum (E-k) dispersion in thevicinity of the Brillouin-zone center for the case of ternary cubicZinc-Gallium-Oxide Zn_(x)Ga_(2(1−x))O_(3−2x), where x=0.5 illustratingthe indirect bandgap at Γ(k=0) in accordance with an illustrativeembodiment of the present disclosure;

FIG. 44O shows an epitaxial layer stack deposited along a growthdirection for the case of an orthorhombic Ga₂O₃ crystal symmetry filmusing an intermediate layer and a prepared substrate surface inaccordance with an illustrative embodiment of the present disclosure;

FIG. 44P shows an experimental HRXRD of two distinctly different crystalsymmetry binary Ga₂O₃ compositions deposited upon a rhombic Sapphireα-Al₂O₃(0001)-oriented substrate controlled via growth conditions inaccordance with an illustrative embodiment of the present disclosure;

FIG. 44Q shows a strain-free energy-crystal momentum (E-k) dispersion inthe vicinity of the Brillouin-zone center for the case of binaryorthorhombic Gallium-Oxide illustrating the direct bandgap at Γ(k=0) inaccordance with an illustrative embodiment of the present disclosure;

FIG. 44R shows an experimental HRXRD and GIXR of two example distinctcompositions of high-quality single crystal corundum symmetry ternary(Al_(x)Ga_(1−x))₂O₃ deposited epitaxially on a bulk (1-100)-orientedcorundum crystal symmetry Al₂O₃ substrate in accordance with anillustrative embodiment of the present disclosure;

FIG. 44S shows an experimental HRXRD of a monoclinic topmost activeGa₂O₃ epilayer deposited upon a ternary Erbium-Gallium-Oxide(Er_(x)Ga_(1−x))₂O₃ transition layer deposited upon a single crystalSilicon (111)-oriented substrate in accordance with an illustrativeembodiment of the present disclosure;

FIG. 44T shows an experimental HRXRD and GIXR of an example high-qualitysingle crystal corundum symmetry binary Ga₂O₃ deposited epitaxially on abulk (11-20)-oriented corundum crystal symmetry Al₂O₃ substrate wherethe two thicknesses of Ga₂O₃ are shown pseudomorphically strained (i.e.,elastic deformation of the bulk Ga₂O₃ unit cell) to the underlying Al₂O₃substrate in accordance with an illustrative embodiment of the presentdisclosure;

FIG. 44U shows an experimental HRXRD and GIXR of an example high-qualitysingle crystal corundum symmetry superlattice comprising bilayers ofbinary pseudomorphic Ga₂O₃ and Al₂O₃ deposited epitaxially on a bulk(11-20)-oriented corundum crystal symmetry Al₂O₃ substrate where thesuperlattice [Al₂O₃/Ga₂O₃] demonstrates the unique properties of thecorundum crystal symmetry in accordance with an illustrative embodimentof the present disclosure;

FIG. 44V shows an experimental transmission electron micrograph (TEM) ofa high-quality single crystal superlattice comprising SL [Al₂O₃/Ga₂O₃]deposited upon a corundum Al₂O₃ substrate depicting the low dislocationdefect density in accordance with an illustrative embodiment of thepresent disclosure;

FIG. 44W shows an experimental HRXRD of a corundum crystal symmetrytopmost active (Al_(x)Ga_(1−x))₂O₃ epilayer deposited upon a singlecorundum Al₂O₃(1-102)-oriented substrate in accordance with anillustrative embodiment of the present disclosure;

FIG. 44X shows an experimental HRXRD and GIXR of an example high-qualitysingle crystal corundum symmetry superlattice comprising bilayers ofternary pseudomorphic (Al_(x)Ga_(1−x))₂O₃ and Al₂O₃ depositedepitaxially on a bulk (1-102)-oriented corundum crystal symmetry Al₂O₃substrate in accordance with an illustrative embodiment of the presentdisclosure, where the superlattice [Al₂O₃/(Al_(x)Ga_(1−x))₂O₃]demonstrates the unique properties of the corundum crystal symmetry;

FIG. 44Y shows an experimental wide angle HRXRD of a cubic crystalsymmetry topmost active Magnesium-Oxide MgO epilayer deposited upon asingle crystal cubic (spinel) Magnesium-Aluminum-Oxide MgAl₂O₄(100)-oriented substrate in accordance with an illustrative embodimentof the present disclosure;

FIG. 44Z shows a strain-free energy-crystal momentum (E-k) dispersion inthe vicinity of the Brillouin-zone center for the case of ternaryMagnesium-Aluminum-Oxide Mg_(x)Al_(2(1−x))O_(3−2x), x=0.5 illustratingthe direct bandgap at Γ(k=0) in accordance with an illustrativeembodiment of the present disclosure;

FIG. 45 shows schematically a construction of epitaxial regions for ametal oxide UVLED comprising a p-i-n heterojunction diode and multiplequantum wells to tune the optical emission energy in accordance with anillustrative embodiment of the present disclosure;

FIG. 46 is an energy band diagram versus growth direction of theepitaxial metal oxide UVLED structure illustrated in FIG. 45 where thek=0 representation of the band structure is plotted in accordance withan illustrative embodiment of the present disclosure;

FIG. 47 shows a spatial carrier confinement structure of the multiplequantum well (MQW) regions of FIG. 46 having quantized electron and holewavefunctions which spatially recombine in the MQW region to generate apredetermined emitted photon energy determined by the respectivequantized states in the conduction and valence bands where the MQWregion has a narrow bandgap material comprising Ga₂O₃ in accordance withan illustrative embodiment of the present disclosure;

FIG. 48 shows a calculated optical absorption spectrum for the devicestructure in FIG. 47 where the lowest energy electron-hole recombinationis determined by the quantized energy levels within the MQW giving riseto sharp and discrete absorption/emission energy in accordance with anillustrative embodiment of the present disclosure;

FIG. 49 is an energy band diagram versus growth direction of anepitaxial metal oxide UVLED structure where the MQW region has a narrowbandgap material comprising (Al_(0.05)Ga_(0.95))₂O₃ in accordance withan illustrative embodiment of the present disclosure;

FIG. 50 shows a calculated optical absorption spectrum for the devicestructure in FIG. 49 where the lowest energy electron-hole recombinationis determined by the quantized energy levels within the MQW giving riseto sharp and discrete absorption/emission energy in accordance with anillustrative embodiment of the present disclosure;

FIG. 51 is an energy band diagram versus growth direction of anepitaxial metal oxide UVLED structure where the MQW region has a narrowbandgap material comprising (Al_(0.1)Ga_(0.9))₂O₃ in accordance with anillustrative embodiment of the present disclosure;

FIG. 52 shows a calculated optical absorption spectrum for the devicestructure in FIG. 49 where the lowest energy electron-hole recombinationis determined by the quantized energy levels within the MQW giving riseto sharp and discrete absorption/emission energy in accordance with anillustrative embodiment of the present disclosure;

FIG. 53 is an energy band diagram versus growth direction of anepitaxial metal oxide UVLED structure where the MQW region has a narrowbandgap material comprising (Al_(0.2)Ga_(0.8))₂O₃ in accordance with anillustrative embodiment of the present disclosure;

FIG. 54 shows a calculated optical absorption spectrum for the devicestructure in FIG. 53 where the lowest energy electron-hole recombinationis determined by the quantized energy levels within the MQW giving riseto sharp and discrete absorption/emission energy in accordance with anillustrative embodiment of the present disclosure;

FIG. 55 plots pure metal work-function energy and sorts the metalspecies from high to low work function for application to p-type andn-type ohmic contacts to metal oxides in accordance with illustrativeembodiments of the present disclosure;

FIG. 56 is a reciprocal lattice map 2-axis x-ray diffraction pattern forpseudomorphic ternary (Al_(0.5)Ga_(0.5))₂O₃ on an A-plane Al₂O₃substrate in accordance with an illustrative embodiment of the presentdisclosure;

FIG. 57 is a 2-axis x-ray diffraction pattern of a pseudomorphic 10period SL [Al₂O₃/Ga₂O₃] on an A-plane Al₂O₃ substrate showing in-planelattice matching throughout the structure in accordance with anillustrative embodiment of the present disclosure;

FIGS. 58A and 58B illustrate optical mode structure and threshold gainfor a slab of metal-oxide semiconductor material in accordance with anillustrative embodiment of the present disclosure;

FIGS. 59A and 59B illustrate optical mode structure and threshold gainfor a slab of metal-oxide semiconductor material in accordance withanother illustrative embodiment of the present disclosure;

FIG. 60 shows an optical cavity formed using an optical gain mediumembedded between two optical reflectors in accordance with anillustrative embodiment of the present disclosure;

FIG. 61 shows an optical cavity formed using an optical gain mediumembedded between two optical reflectors in accordance with anillustrative embodiment of the present disclosure, illustrating that twooptical wavelengths can be supported by the gain medium and cavitylength;

FIG. 62 shows an optical cavity formed using an optical gain medium offinite thickness embedded between two optical reflectors and positionedat the peak electric field intensity of a fundamental wavelength mode inaccordance with an illustrative embodiment of the present disclosure,showing that only one optical wavelength can be supported by the gainmedium and cavity length;

FIG. 63 shows an optical cavity formed using two optical gain media offinite thickness embedded between two optical reflectors in accordancewith an illustrative embodiment that is positioned at the peak electricfield intensity of a shorter wavelength mode, illustrating that only oneoptical wavelength can be supported by the gain medium and cavitylength;

FIGS. 64A and 64B show single quantum well structures comprisingmetal-oxide ternary materials with quantized electron and holes statesin accordance with an illustrative embodiment of the present disclosuredepicting two different quantum well thicknesses;

FIGS. 65A and 65B show single quantum well structures comprisingmetal-oxide ternary materials with quantized electron and hole states inaccordance with an illustrative embodiment of the present disclosuredepicting two different quantum well thicknesses;

FIG. 66 shows spontaneous emission spectra from the quantum wellstructures disclosed in FIGS. 64A, 64B, 65A and 65B;

FIG. 67A and FIG. 67B show a spatial energy band structure of a metaloxide quantum well and the associated energy-crystal momentum bandstructure in accordance with an illustrative embodiment of the presentdisclosure;

FIGS. 68A and 68B show a population inversion mechanism for theelectrons and holes in a quantum well band structure and the resultinggain spectrum for the quantum well;

FIGS. 69A and 69B show electron and hole energy states for filledconduction and valence bands in the energy-momentum space for the caseof a direct and pseudo-direct bandgap metal oxide structure inaccordance with an illustrative embodiment of the present disclosure;

FIGS. 70A and 70B show an impact ionization process for metal oxideinjected hot electrons resulting in pair production in accordance withan illustrative embodiment of the present disclosure;

FIGS. 71A and 71B show an impact ionization process for metal oxideinjected hot electrons resulting in pair production in accordance withanother illustrative embodiment of the present disclosure;

FIGS. 72A and 72B show an effect of an electric field applied to metaloxide creating a plurality of impact ionization events in accordancewith another illustrative embodiment of the present disclosure;

FIG. 73 shows a vertical type ultraviolet laser structure in accordancewith an illustrative embodiment of the present disclosure where thereflectors form part of the cavity and electrical circuit;

FIG. 74 shows a vertical type ultraviolet laser structure in accordancewith an illustrative embodiment of the present disclosure where thereflectors forming the optical cavity are decoupled from the electricalcircuit; and

FIG. 75 shows a waveguide type ultraviolet laser structure in accordancewith an illustrative embodiment of the present disclosure where thereflectors forming the optical cavity are decoupled from the electricalcircuit and where the optical gain medium embedded within the lateralcavity can have a length optimized for a low threshold gain.

In the following description, like reference characters designate likeor corresponding parts throughout the figures.

DETAILED DESCRIPTION

Disclosed herein are embodiments of an optoelectronic semiconductorlight emitting device that may be configured to emit light having awavelength in the range of from about 150 nm to about 280 nm. Thedevices comprise a metal oxide substrate having at least one epitaxialsemiconductor metal oxide layer disposed thereon. The substrate maycomprise Al₂O₃, Ga₂O₃, MgO, LiF, MgAl₂O₄, MgGa₂O₄, LiGaO₂, LiAlO₂,(Al_(x)Ga_(1−x))₂O₃, MgF₂, LaAlO₃, TiO₂ or quartz. In certainembodiments, the one or more of the at least one semiconductor layercomprises at least one of Al₂O₃ and Ga₂O₃.

In a first aspect, the present disclosure provides an optoelectronicsemiconductor light emitting device configured to emit light having awavelength in the range from about 150 nm to about 280 nm, the devicecomprising a substrate having at least one epitaxial semiconductor layerdisposed thereon, wherein each of the one or more epitaxialsemiconductor layers comprises a metal oxide.

In another form, the metal oxide of each of the one or moresemiconductor layers is selected from the group consisting of Al₂O₃,Ga₂O₃, MgO, NiO, LiO₂, ZnO, SiO₂, GeO, Er₂O₃, Gd₂O₃, PdO, Bi₂O₃, IrO₂,and any combination of the aforementioned metal oxides.

In another form, at least one of the one or more semiconductor layers isa single crystal.

In another form, the at least one of the one or more semiconductorlayers has rhombohedral, hexagonal or monoclinic crystal symmetry.

In another form, at least one of the one or more semiconductor layers iscomposed of a binary metal oxide, wherein the metal oxide is selectedfrom Al₂O₃ and Ga₂O₃.

In another form, at least one of the one or more semiconductor layers iscomposed of a ternary metal-oxide composition, and the ternary metaloxide composition comprises at least one of Al₂O₃ and Ga₂O₃, and,optionally, a metal oxide selected from MgO, NiO, LiO₂, ZnO, SiO₂, GeO,Er₂O₃, Gd₂O₃, PdO, Bi₂O₃, and IrO₂.

In another form, the at least one of the one or more semiconductorlayers is composed of a ternary metal-oxide composition of(Al_(x)Ga_(1−x))₂O₃ wherein 0<x<1.

In another form, the at least one of the one or more semiconductorlayers comprises uniaxially deformed unit cells.

In another form, the at least one of the one or more semiconductorlayers comprises biaxially deformed unit cells.

In another form, the at least one of the one or more semiconductorlayers comprises triaxially deformed unit cells.

In another form, the at least one of the one or more semiconductor layeris composed of a quaternary metal oxide composition, and the quaternarymetal oxide composition comprises either: (i) Ga₂O₃ and a metal oxideselected from Al₂O₃, MgO, NiO, LiO₂, ZnO, SiO₂, GeO₂, Er₂O₃, Gd₂O₃, PdO,Bi₂O₃, and IrO₂; or (ii) Al₂O₃ and a metal oxide selected from Ga₂O₃,MgO, NiO, LiO₂, ZnO, SiO₂, GeO₂, Er₂O₃, Gd₂O₃, PdO, Bi₂O₃, and IrO₂.

In another form, the at least one of the one or more semiconductorlayers is composed of a quaternary metal oxide composition(Ni_(x)Mg_(1−x))_(y)Ga_(2(1−y))O_(3−2y) where 0<x<1 and 0<y<1.

In another form, the surface of the substrate is configured to enablelattice matching of crystal symmetry of the at least one semiconductorlayer.

In another form, the substrate is a single crystal substrate.

In another form, the substrate is selected from Al₂O₃, Ga₂O₃, MgO, LiF,MgAl₂O₄, MgGa₂O₄, LiGaO₂, LiAlO₂, MgF₂, LaAlO₃, TiO₂ and quartz.

In another form, the surface of the substrate has crystal symmetry andin-plane lattice constant matching so as to enable homoepitaxy orheteroepitaxy of the at least one semiconductor layer.

In another form, one or more of the at least one semiconductor layer isof direct bandgap type.

In a second aspect, the present disclosure provides an optoelectronicsemiconductor device for generating light of a predetermined wavelengthcomprising a substrate; and an optical emission region having an opticalemission region band structure configured for generating light of thepredetermined wavelength and comprising one or more epitaxial metaloxide layers supported by the substrate.

In another form, configuring the optical emission region band structurefor generating light of the predetermined wavelength comprises selectingthe one or more epitaxial metal oxide layers to have an optical emissionregion band gap energy capable of generating light of the predeterminedwavelength.

In another form, selecting the one or more epitaxial metal oxide layersto have an optical emission region band gap energy capable of generatinglight of the predetermined wavelength comprises forming the one or moreepitaxial metal oxide layers of a binary metal oxide of the formA_(x)O_(y) comprising a metal specie (A) combined with oxygen (O) in therelative proportions x and y.

In another form, the binary metal oxide is Al₂O₃.

In another form, the binary metal oxide is Ga₂O₃.

In another form, the binary metal oxide is selected from the groupconsisting of MgO, NiO, LiO₂, ZnO, SiO₂, GeO, Er₂O₃, Gd₂O₃, PdO, Bi₂O₃and IrO₂.

In another form, selecting the one or more epitaxial metal oxide layersto have an optical emission region band gap energy capable of generatinglight of the predetermined wavelength comprises forming the one or moreepitaxial metal oxide layers of a ternary metal oxide.

In another form, the ternary metal oxide is a ternary metal oxide bulkalloy of the form A_(x)B_(y)O_(n) comprising a metal species (A) and (B)combined with oxygen (O) in the relative proportions x, y and n.

In another form, a relative fraction of the metal specie B to the metalspecie A ranges from a minority relative fraction to a majority relativefraction.

In another form, the ternary metal oxide is of the formA_(x)B_(1−x)O_(n) where 0<x<1.0.

In another form, the metal specie A is Al and metal specie B is selectedfrom the group consisting of: Zn, Mg, Ga, Ni, Rare Earth, Ir Bi, and Li.

In another form, the metal specie A is Ga and metal specie B is selectedfrom the group consisting of: Zn, Mg, Ni, Al, Rare Earth, Ir, Bi and Li.

In another form, the ternary metal oxide is of the form(Al_(x)Ga_(1−x))₂O₃, where 0<x<1. In other forms, x is about 0.1, orabout 0.3, or about 0.5.

In another form, the ternary metal oxide is a ternary metal oxideordered alloy structure formed by sequential deposition of unit cellsformed along a unit cell direction and comprising alternating layers ofmetal specie A and metal specie B having intermediate 0 layers to form ametal oxide ordered alloy of the form A-O—B—O-A-O—B-etc.

In another form, the metal specie A is Al and the metal specie B is Ga,and the ternary metal oxide ordered alloy is of the formAl—O—Ga—O—Al-etc.

In another form, the ternary metal oxide is of the form of a host binarymetal oxide crystal with a crystal modification specie.

In another form, the host binary metal oxide crystal is selected fromthe group consisting of Ga₂O₃, Al₂O₃, MgO, NiO, ZnO, Bi₂O₃, r-GeO₂,Ir₂O₃, RE₂O₃ and Li₂O and the crystal modification specie is selectedfrom the group consisting of Ga, Al, Mg, Ni, Zn, Bi, Ge, Ir, RE and Li.

In another form, selecting the one or more epitaxial metal oxide layersto have an optical emission region band gap energy capable of generatinglight of the predetermined wavelength comprises forming the one or moreepitaxial metal oxide layers as a superlattice comprising two or morelayers of metal oxides forming a unit cell and repeating with a fixedunit cell period along a growth direction.

In another form, the superlattice is a bi-layered superlatticecomprising repeating layers comprising two different metal oxides.

In another form, the two different metal oxides comprise a first binarymetal oxide and a second binary metal oxide.

In another form, the first binary metal oxide is Al₂O₃ and the secondbinary metal oxide is Ga₂O₃.

In another form, the first binary metal oxide is NiO and the secondbinary metal oxide is Ga₂O₃.

In another form, the first binary metal oxide is MgO and the secondbinary metal oxide is NiO.

In another form, the first binary metal oxide is selected from the groupconsisting of Al₂O₃, Ga₂O₃, MgO, NiO, LiO₂, ZnO, SiO₂, GeO, Er₂O₃,Gd₂O₃, PdO, Bi₂O₃ and IrO₂ and wherein the second binary metal oxide isselected from the group consisting of Al₂O₃, Ga₂O₃, MgO, NiO, LiO₂, ZnO,SiO₂, GeO, Er₂O₃, Gd₂O₃, PdO, Bi₂O₃ and IrO₂ absent the first selectedbinary metal oxide.

In another form, the two different metal oxides comprise a binary metaloxide and a ternary metal oxide.

In another form, the binary metal oxide is Ga₂O₃ and the ternary metaloxide is (Al_(x)Ga_(1−x))₂O₃, where 0<x<1.0.

In another form, the binary metal oxide is Ga₂O₃ and the ternary metaloxide is Al_(x)Ga_(1−x)O₃, where 0<x<1.0.

In another form, the binary metal oxide is Ga₂O₃ and the ternary metaloxide is Mg_(x)Ga_(2(1−x))O_(3−2x), where 0<x<1.0.

In another form, the binary metal oxide is Al₂O₃ and the ternary metaloxide is (Al_(x)Ga_(1−x))₂O₃, where 0<x<1.0.

In another form, the binary metal oxide is Al₂O₃ and the ternary metaloxide is Al_(x)Ga_(1−x)O₃, where 0<x<1.0.

In another form, the binary metal oxide is Al₂O₃ and the ternary metaloxide is (Al_(x)Er_(1−x))₂O₃.

In another form, the ternary metal oxide is selected from the groupconsisting of (Ga_(2x)Ni_(1−x))O_(2x+1), (Al_(2x)Ni_(1−x))O_(2x+1),(Al_(2x)Mg_(1−x))O_(2x+1), (Ga_(2x)Mg_(1−x))O_(2x+1),(Al_(2x)Zn_(1−x))O_(2x+1), (Ga_(2x)Zn_(1−x))O_(2x+1),(Ga_(x)Bi_(1−x))₂O₃, (Al_(x)Bi_(1−x))₂O₃, (Al_(2x)Ge_(1−x))O_(2+x),(Ga_(2x)Ge_(1−x))O_(2+x), (Al_(x)Ir_(1−x))₂O₃, (Ga_(x)Ir_(1−x))₂O₃,(Ga_(x)RE_(1−x))O₃, (Al_(x)RE_(1−x))O₃, (Al_(2x)Li_(2(1−x)))O_(2x+1) and(Ga_(2x)Li_(2(1−x)))O_(2x+1), where 0<x<1.0.

In another form, the binary metal oxide is selected from the groupconsisting of Al₂O₃, Ga₂O₃, MgO, NiO, LiO₂, ZnO, SiO₂, GeO, Er₂O₃,Gd₂O₃, PdO, Bi₂O₃ and IrO₂.

In another form, the two different metal oxides comprise a first ternarymetal oxide and a second ternary metal oxide.

In another form, the first ternary metal oxide is Al_(x)Ga_(1−x)O andthe second ternary metal oxide is (Al_(x)Ga_(1−x))₂O₃ orAl_(y)Ga_(1−y)O₃ where 0<x<1 and 0<y<1.

In another form, the first ternary metal oxide is (Al_(x)Ga_(1−x))₂O₃and the second ternary metal oxide is (Al_(y)Ga_(1−y))₂O₃, where 0<x<1and 0<y<1.

In another form, the first ternary metal oxide is selected from thegroup consisting of (Ga_(2x)Ni_(1−x))O_(2x+1),(Al_(2x)Ni_(1−x))O_(2x+1), (Al_(2x)Mg_(1−x))O_(2x+1),(Ga_(2x)Mg_(1−x))O_(2x+1), (Al_(2x)Zn_(1−x))O_(2x+1),(Ga_(2x)Zn_(1−x))O_(2x+1), (Ga_(x)Bi_(1−x))₂O₃, (Al_(x)Bi_(1−x))₂O₃,(Al_(2x)Ge_(1−x))O_(2+x), (Ga_(2x)Ge_(1−x))O_(2+x), (Al_(x)Ir_(1−x))₂O₃,(Ga_(x)Ir_(1−x))₂O₃, (Ga_(x)RE_(1−x))O₃, (Al_(x)RE_(1−x))O₃,(Al_(2x)Li_(2(1−x)))O_(2x+1) and (Ga_(2x)Li_(2(1−x)))O_(2x+1), andwherein the second ternary metal oxide is selected from the groupconsisting of (Ga_(2x)N_(1−x))O_(2x+1), (Al_(2x)Ni_(1−x))O_(2x+1),(Al_(2x)Mg_(1−x))O_(2x+1), (Ga_(2x)Mg_(1−x))O_(2x+1),(Al_(2x)Zn_(1−x))O_(2x+1), (Ga_(2x)Zn_(1−x))O_(2x+1),(Ga_(x)Bi_(1−x))₂O₃, (Al_(x)Bi_(1−x))₂O₃, (Al_(2x)Ge_(1−x))O_(2+x),(Ga_(2x)Ge_(1−x))O_(2+x), (Al_(x)Ir_(1−x))₂O₃, (Ga_(x)Ir_(1−x))₂O₃,(Ga_(x)RE_(1−x))O₃, (Al_(x)RE_(1−x))O₃, (Al_(2x)Li_(2(1−x)))O_(2x+1),and (Ga_(2x)Li_(2(1−x)))O_(2x+1) absent the first selected ternary metaloxide, where 0<x<1.0.

In another form, the superlattice is a tri-layered superlatticecomprising repeating layers of three different metal oxides.

In another form, the three different metal oxides comprise a firstbinary metal oxide, a second binary metal oxide and a third binary metaloxide.

In another form, the first binary metal oxide is MgO, the second binarymetal oxide is NiO and the third binary metal oxide Ga₂O₃.

In another form, the first binary metal oxide is selected from the groupconsisting of Al₂O₃, Ga₂O₃, MgO, NiO, LiO₂, ZnO, SiO₂, GeO, Er₂O₃,Gd₂O₃, PdO, Bi₂O₃ and IrO₂, and wherein the second binary metal oxide isselected from the group Al₂O₃, Ga₂O₃, MgO, NiO, LiO₂, ZnO, SiO₂, GeO,Er₂O₃, Gd₂O₃, PdO, Bi₂O₃ and IrO₂ absent the first selected binary metaloxide, and wherein the third binary metal oxide is selected from thegroup Al₂O₃, Ga₂O₃, MgO, NiO, LiO₂, ZnO, SiO₂, GeO, Er₂O₃, Gd₂O₃, PdO,Bi₂O₃ and IrO₂ absent the first and second selected binary metal oxides.

In another form, the three different metal oxides comprise a firstbinary metal oxide, a second binary metal oxide and a ternary metaloxide.

In another form, the first binary metal oxide is selected from the groupconsisting of Al₂O₃, Ga₂O₃, MgO, NiO, LiO₂, ZnO, SiO₂, GeO, Er₂O₃,Gd₂O₃, PdO, Bi₂O₃ and IrO₂, and wherein the second binary metal oxide isselected from the group consisting of Al₂O₃, Ga₂O₃, MgO, NiO, LiO₂, ZnO,SiO₂, GeO, Er₂O₃, Gd₂O₃, PdO, Bi₂O₃ and IrO₂ absent the first selectedbinary metal oxide, and wherein the ternary metal oxide is selected fromthe group consisting of (Ga_(2x)Ni_(1−x))O_(2x+1),(Al_(2x)Ni_(1−x))O_(2x+1), (Al_(2x)Mg_(1−x))O_(2x+1),(Ga_(2x)Mg_(1−x))O_(2x+1), (Al_(2x)Zn_(1−x))O_(2x+1),(Ga_(2x)Zn_(1−x))O_(2x+1), (Ga_(x)Bi_(1−x))₂O₃, (Al_(x)Bi_(1−x))₂O₃,(Al_(2x)Ge_(1−x))O_(2+x), (Ga_(2x)Ge_(1−x))O_(2+x), (Al_(x)Ir_(1−x))₂O₃,(Ga_(x)Ir_(1−x))₂O₃, (Ga_(x)RE_(1−x))O₃, (Al_(x)RE_(1−x))O₃,(Al_(2x)Li_(2(1−x)))O_(2x+1) and (Ga_(2x)Li_(2(1−x)))O_(2x+1), where0<x<1.

In another form, the three different metal oxides comprise a binarymetal oxide, a first ternary metal oxide and a second ternary metaloxide.

In another form, the binary metal oxide is selected from the groupconsisting of Al₂O₃, Ga₂O₃, MgO, NiO, LiO₂, ZnO, SiO₂, GeO, Er₂O₃,Gd₂O₃, PdO, Bi₂O₃ and IrO₂, and wherein the first ternary metal oxide isselected from the group consisting of (Ga_(2x)Ni_(1−x))O_(2x+1),(Al_(2x)Ni_(1−x))O_(2x+1), (Al_(2x)Mg_(1−x))O_(2x+1),(Ga_(2x)Mg_(1−x))O_(2x+1), (Al_(2x)Zn_(1−x))O_(2x+1),(Ga_(2x)Zn_(1−x))O_(2x+1), (Ga_(x)Bi_(1−x))₂O₃, (Al_(x)Bi_(1−x))₂O₃,(Al_(2x)Ge_(1−x))O_(2+x), (Ga_(2x)Ge_(1−x))O_(2+x), (Al_(x)Ir_(1−x))₂O₃,(Ga_(x)Ir_(1−x))₂O₃, (Ga_(x)RE_(1−x))O₃, (Al_(x)RE_(1−x))O₃,(Al_(2x)Li_(2(1−x)))O_(2x+1) and (Ga_(2x)Li_(2(1−x)))O_(2x+1), andwherein the second ternary metal oxide is selected from the groupconsisting of (Ga_(2x)Ni_(1−x))O_(2x+1), (Al_(2x)Ni_(1−x))O_(2x+1),(Al_(2x)Mg_(1−x))O_(2x+1), (Ga_(2x)Mg_(1−x))O_(2x+1),(Al_(2x)Zn_(1−x))O_(2x+1), (Ga_(2x)Zn_(1−x))O_(2x+1),(Ga_(x)Bi_(1−x))₂O₃, (Al_(x)Bi_(1−x))₂O₃, (Al_(2x)Ge_(1−x))O_(2+x),(Ga_(2x)Ge_(1−x))O_(2+x), (Al_(x)Ir_(1−x))₂O₃, (Ga_(x)Ir_(1−x))₂O₃,(Ga_(x)RE_(1−x))O₃, (Al_(x)RE_(1−x))O₃, (Al_(2x)Li_(2(1−x)))O_(2x+1) and(Ga_(2x)Li_(2(1−x)))O_(2x+1) absent the first selected ternary metaloxide, where 0<x<1.

In another form, the three different metal oxides comprise a firstternary metal oxide, a second ternary metal oxide and a third ternarymetal oxide.

In another form, the first ternary metal oxide is selected from thegroup consisting of (Ga_(2x)Ni_(1−x))O_(2x+1),(Al_(2x)Ni_(1−x))O_(2x+1), (Al_(2x)Mg_(1−x))O_(2x+1),(Ga_(2x)Mg_(1−x))O_(2x+1), (Al_(2x)Zn_(1−x))O_(2x+1),(Ga_(2x)Zn_(1−x))O_(2x+1), (Ga_(x)Bi_(1−x))₂O₃, (Al_(x)Bi_(1−x))₂O₃,(Al_(2x)Ge_(1−x))O_(2+x), (Ga_(2x)Ge_(1−x))O_(2+x), (Al_(x)Ir_(1−x))₂O₃,(Ga_(x)Ir_(1−x))₂O₃, (Ga_(x)RE_(1−x))O₃, (Al_(x)RE_(1−x))O₃,(Al_(2x)Li_(2(1−x)))O_(2x+1) and (Ga_(2x)Li_(2(1−x)))O_(2x+1), andwherein the second ternary metal oxide is selected from the groupconsisting of (Ga_(2x)Ni_(1−x))O_(2x+1), (Al_(2x)Ni_(1−x))O_(2x+1),(Al_(2x)Mg_(1−x))O_(2x+1), (Ga_(2x)Mg_(1−x))O_(2x+1),(Al_(2x)Zn_(1−x))O_(2x+1), (Ga_(2x)Zn_(1−x))O_(2x+1),(Ga_(x).Bi_(1−x))₂O₃, (Al_(x)Bi_(1−x))₂O₃, (Al_(2x)Ge_(1−x))O_(2+x),(Ga_(2x)Ge_(1−x))O_(2+x), (Al_(x)Ir_(1−x))₂O₃, (Ga_(x)Ir_(1−x))₂O₃,(Ga_(x)RE_(1−x))O₃, (Al_(x)RE_(1−x))O₃, (Al_(2x)Li_(2(1−x)))O_(2x+1) and(Ga_(2x)Li_(2(1−x)))O_(2x+1) absent the first selected ternary metaloxide, and wherein the third ternary metal oxide is selected from thegroup consisting of (Ga_(2x)N_(1−x))O_(2x+1), (Al_(2x)Ni_(1−x))O_(2x+1),(Al_(2x)Mg_(1−x))O_(2x+1), (Ga_(2x)Mg_(1−x))O_(2x+1),(Al_(2x)Zn_(1−x))O_(2x+1), (Ga_(2x)Zn_(1−x))O_(2x+1),(Ga_(x)Bi_(1−x))₂O₃, (Al_(x)Bi_(1−x))₂O₃, (Al_(2x)Ge_(1−x))O_(2+x),(Ga_(2x)Ge_(1−x))O_(2+x), (Al_(x)Ir_(1−x))₂O₃, (Ga_(x)Ir_(1−x))₂O₃,(Ga_(x)RE_(1−x))O₃, (Al_(x)RE_(1−x))O₃, (Al_(2x)Li_(2(1−x)))O_(2x+1) and(Ga_(2x)Li_(2(1−x)))O_(2x+1) absent the first and second selectedternary metal oxides, where 0<x<1.

In another form, the superlattice is a quad-layered superlatticecomprising repeating layers of at least three different metal oxides.

In another form, the superlattice is a quad-layered superlatticecomprising repeating layers of three different metal oxides, and aselected metal oxide layer of the three different metal oxides isrepeated in the quad-layered superlattice.

In another form, the three different metal oxides comprise a firstbinary metal oxide, a second binary metal oxide and a third binary metaloxide.

In another form, the first binary metal oxide is MgO, the second binarymetal oxide is NiO and the third binary metal oxide is Ga₂O₃ forming aquad-layer superlattice comprising MgO—Ga₂O₃—NiO—Ga₂O₃ layers.

In another form, the three different metal oxides are selected from thegroup of consisting of Al₂O₃, Ga₂O₃, MgO, NiO, LiO₂, ZnO, SiO₂, GeO,Er₂O₃, Gd₂O₃, PdO, Bi₂O₃, IrO₂. (Ga_(2x)Ni_(1−x))O_(2x+1),(Al_(2x)Ni_(1−x))O_(2x+1), (Al_(2x)Mg_(1−x))O_(2x+1),(Ga_(2x)Mg_(1−x))O_(2x+1), (Al_(2x)Zn_(1−x))O_(2x+1),(Ga_(2x)Zn_(1−x))O_(2x+1), (Ga_(x)Bi_(1−x))₂O₃, (Al_(x)Bi_(1−x))₂O₃,(Al_(2x)Ge_(1−x))O_(2+x), (Ga_(2x)Ge_(1−x))O_(2+x), (Al_(x)Ir_(1−x))₂O₃,(Ga_(x)Ir_(1−x))₂O₃, (Ga_(x)RE_(1−x))O₃, (Al_(x)RE_(1−x))O₃,(Al_(2x)Li_(2(1−x)))O_(2x+1) and (Ga_(2x)Li_(2(1−x)))O_(2x+1), where0<x<1.0.

In another form, the superlattice is a quad-layered superlatticecomprising repeating layers of four different metal oxides.

In another form, the four different metal oxides are selected from thegroup of consisting of Al₂O₃, Ga₂O₃, MgO, NiO, LiO₂, ZnO, SiO₂, GeO,Er₂O₃, Gd₂O₃, PdO, Bi₂O₃, IrO₂, (Ga_(2x)Ni_(1−x))O_(2x+1),(Al_(2x)Ni_(1−x))O_(2x+1), (Al_(2x)Mg_(1−x))O_(2x+1),(Ga_(2x)Mg_(1−x))O_(2x+1), (Al_(2x)Zn_(1−x))O_(2x+1),(Ga_(2x)Zn_(1−x))O_(2x+1), (Ga_(x)Bi_(1−x))₂O₃, (Al_(x)Bi_(1−x))₂O₃,(Al_(2x)Ge_(1−x))O_(2+x), (Ga_(2x)Ge_(1−x))O_(2+x), (Al_(x)Ir_(1−x))₂O₃,(Ga_(x)Ir_(1−x))₂O₃, (Ga_(x)RE_(1−x))O₃, (Al_(x)RE_(1−x))O₃,(Al_(2x)Li_(2(1−x)))O_(2x+1) and (Ga_(2x)Li_(2(1−x)))O_(2x+1), where0<x<1.0.

In another form, respective individual layers of the two or more metaloxide layers forming the unit cell of the superlattice have a thicknessless than or approximately equal to an electron de Broglie wavelength inthat respective individual layer.

In another form, configuring the optical emission region band structurefor generating light of the predetermined wavelength comprises modifyingan initial optical emission region band structure of the one or moreepitaxial metal oxide layers on forming the optoelectronic device.

In another form, modifying the initial optical emission region bandstructure of the one or more epitaxial metal oxide layers on forming theoptoelectronic device comprises introducing a predetermined strain tothe one or more epitaxial metal oxide layers during epitaxial depositionof the one or more epitaxial metal oxide layers.

In another form, the predetermined strain is introduced to modify theinitial optical emission region band structure from an indirect band gapto a direct band gap.

In another form, the predetermined strain is introduced to modify aninitial bandgap energy of the initial optical emission region bandstructure.

In another form, the predetermined strain is introduced to modify aninitial valence band structure of the initial optical emission regionband structure.

In another form, modifying the initial valence band structure comprisesraising or lowering a selected valence band with respect to the Fermienergy level of the optical emission region.

In another form, modifying the initial valence band structure comprisesmodifying the shape of the valence band structure to change localizationcharacteristics of holes formed in the optical emission region.

In another form, introducing the predetermined strain to the one or moreepitaxial metal oxide layers comprises selecting a to be strained metaloxide layer having a composition and crystal symmetry type which, whenepitaxially formed on an underlying layer having a underlying layercomposition and crystal symmetry type, will introduce the predeterminedstrain into the to be strained metal oxide layer.

In another form, the predetermined strain is a biaxial strain.

In another form, the underlying layer is a metal oxide having a firstcrystal symmetry type and the to be strained metal oxide layer also hasthe first crystal symmetry type but with a different lattice constant tointroduce the biaxial strain into the to be strained metal oxide layer.

In another form, the underlying layer of metal oxide is Ga₂O₃ and the tobe strained metal oxide layer is Al₂O₃, and biaxial compression isintroduced into the Al₂O₃ layer.

In another form, the underlying layer of metal oxide is Al₂O₃ and the tobe strained layer of metal oxide is Ga₂O₃, and biaxial tension isintroduced into the Ga₂O₃ layer.

In another form, the predetermined strain is a uniaxial strain.

In another form, the underlying layer has a first crystal symmetry typehaving asymmetric unit cells.

In another form, the to be strained metal oxide layer is monoclinicGa₂O₃, Al_(x)Ga_(1−x)O or Al₂O₃, where x<0<1.

In another form, the underlying layer and the to be strained layer formlayers in a superlattice.

In another form, modifying an initial optical emission region bandstructure of the one or more epitaxial metal oxide layers on forming theoptoelectronic device comprises introducing a predetermined strain tothe one or more epitaxial metal oxide layers following epitaxialdeposition of the one or more epitaxial metal oxide layers.

In another form, the optoelectronic device comprises a firstconductivity type region comprising one or more epitaxial metal oxidelayers having a first conductivity type region band structure configuredto operate in combination with the optical emission region to generatelight of the predetermined wavelength.

In another form, configuring the first conductivity type region bandstructure to operate in combination with the optical emission region togenerate light of the predetermined wavelength comprises selecting afirst conductivity type region energy band gap greater than the opticalemission region energy band gap.

In another form, configuring the first conductivity type region bandstructure to operate in combination with the optical emission region togenerate light of the predetermined wavelength comprises selecting thefirst conductivity type region to have an indirect bandgap.

In another form, configuring the first conductivity type region bandstructure comprises one or more of: selecting an appropriate metal oxidematerial or materials in line with the principles and techniquesconsidered in the present disclosure in relation to the optical emissionregion; forming a superlattice in line with the principles andtechniques considered in the present disclosure in relation to theoptical emission region; and/or modifying the first conductivity typeregion band structure by applying strain in line with the principles andtechniques considered in the present disclosure in relation to theoptical emission region.

In another form, the first conductivity type region is a n-type region.

In another form, the optoelectronic device comprises a secondconductivity type region comprising one or more epitaxial metal oxidelayers having a second conductivity type region band structureconfigured to operate in combination with the optical emission regionand the first conductivity type region to generate light of thepredetermined wavelength.

In another form, configuring the second conductivity type region bandstructure to operate in combination with the optical emission region togenerate light of the predetermined wavelength comprises selecting asecond conductivity type region energy band gap greater than the opticalemission region energy band gap.

In another form, configuring the second conductivity type region bandstructure to operate in combination with the optical emission region togenerate light of the predetermined wavelength comprises selecting thesecond conductivity type region to have an indirect bandgap.

In another form, configuring the second conductivity type region bandstructure comprises one or more of: selecting an appropriate metal oxidematerial or materials in line with the principles and techniquesconsidered in the present disclosure in relation to the optical emissionregion; forming a superlattice in line with the principles andtechniques considered in the present disclosure in relation to theoptical emission region; and/or modifying the first conductivity typeregion band structure by applying strain in line with the principles andtechniques considered in the present disclosure in relation to theoptical emission region.

In another form, the second conductivity type region is a p-type region.

In another form, the substrate is formed from a metal oxide.

In another form, the metal oxide is selected from the group consistingof Al₂O₃, Ga₂O₃, MgO, LiF, MgAl₂O₄, MgGa₂O₄, LiGaO₂, LiAlO₂,(Al_(x)Ga_(1−x))₂O₃, LaAlO₃, TiO₂ and quartz.

In another form, the substrate is formed from a metal fluoride.

In another form, the metal fluoride is MgF₂ or LiF.

In another form, the predetermined wavelength is in the wavelength rangeof 150 nm to 700 nm.

In another form, the predetermined wavelength is in the wavelength rangeof 150 nm to 280 nm.

In a third aspect, the present disclosure provides a method for formingan optoelectronic semiconductor device configured to emit light having awavelength in the range from about 150 nm to about 280 nm, the methodcomprising: providing a metal oxide substrate having an epitaxial growthsurface; oxidizing the epitaxial growth surface to form an activatedepitaxial growth surface; and exposing the activated epitaxial growthsurface to one or more atomic beams each comprising high purity metalatoms and one or more atomic beams comprising oxygen atoms underconditions to deposit two or more epitaxial metal oxide films.

In another form, the metal oxide substrate comprises an Al or a Ga metaloxide substrate.

In another form, the one or more atomic beams each comprising highpurity metal atoms comprise any one or more of the metals selected fromthe group consisting of Al, Ga. Mg, Ni, Li, Zn, Si, Ge, Er, Gd, Pd, Bi,Ir, and any combination of the aforementioned metals.

In another form, the one or more atomic beams each comprising highpurity metal atoms comprise any one or more of the metals selected fromthe group consisting of Al and Ga, and the epitaxial metal oxide filmscomprise (Al_(x)Ga_(1−x))₂O₃, wherein 0≤x≤1.

In another form, the conditions to deposit two or more epitaxial metaloxide films comprise exposing the activated epitaxial growth surface toatomic beams comprising high purity metal atoms and atomic beamscomprising oxygen atoms at an oxygen:total metal flux ratio of >1.

In another form, at least one of the two or more epitaxial metal oxidefilms provides a first conductivity type region comprising one or moreepitaxial metal oxide layers, and at least another of the two or moreepitaxial metal oxide films provides a second conductivity type regioncomprising one or more epitaxial metal oxide layers.

In another form, at least one of the two or more epitaxial(Al_(x)Ga_(1−x))₂O₃ films provides a first conductivity type regioncomprising one or more epitaxial (Al_(x)Ga_(1−x))₂O₃ layers, and atleast another of the two or more epitaxial (Al_(x)Ga_(1−x))₂O₃ filmsprovides a second conductivity type region comprising one or moreepitaxial (Al_(x)Ga_(1−x))₂O₃ layers.

In another form, the substrate is treated prior to the oxidizing step byhigh temperature (>800° C.) desorption in an ultrahigh vacuum chamber(less than 5×10⁻¹⁰ Torr) to form an atomically flat epitaxial growthsurface.

In another form, the method further comprises monitoring the surface inreal-time to assess atomic surface quality.

In another form, the surface is monitored in real-time by reflectionhigh energy electron diffraction (RHEED).

In another form, oxidizing the epitaxial growth surface comprisesexposing the epitaxial growth surface to an oxygen source underconditions to oxidize the epitaxial growth surface.

In another form, the oxygen source is selected from one or more of thegroup consisting of an oxygen plasma, ozone and nitrous oxide.

In another form, the oxygen source is radiofrequency inductively coupledplasma (RF-ICP).

In another form, the method further comprises monitoring the surface inreal-time to assess surface oxygen density.

In another form, the surface is monitored in real-time by RHEED.

In another form, the atomic beams comprising high purity Al atoms and/orhigh purity Ga atoms are each provided by effusion cells comprisinginert ceramic crucibles radiatively heated by a filament and controlledby feedback sensing to monitor the metal melt temperature within thecrucible.

In another form, high purity elemental metals of 6N to 7N or higherpurity are used.

In another form, the method further comprises measuring the beam flux ofeach Al and/or Ga and oxygen atomic beam to determine the relative fluxratio prior to exposing the activated epitaxial growth surface to theatomic beams at the determined relative flux ratio.

In another form, the method further comprises rotating the substrate asthe activated epitaxial growth surface is exposed to the atomic beams soas to accumulate a uniform amount of atomic beam intersecting thesubstrate surface for a given amount of deposition time.

In another form, the method further comprises heating the substrate asthe activated epitaxial growth surface is exposed to the atomic beams.

In another form, the substrate is heated radiatively from behind using ablackbody emissivity matched to the below bandgap absorption of themetal oxide substrate.

In another form, the activated epitaxial growth surface is exposed tothe atomic beams in a vacuum of from about 1×10⁻⁶ Torr to about 1×10⁻⁵Torr.

In another form, Al and Ga atomic beam fluxes at the substrate surfaceare from about 1×10⁻⁸ Torr to about 1×10⁻⁶ Torr.

In another form, oxygen atomic beam fluxes at the substrate surface arefrom about 1×10⁻⁷ Torr to about 1×10⁻⁵ Torr.

In another form, the Al or Ga metal oxide substrate is A-plane sapphire.

In another form, the Al or Ga metal oxide substrate is monoclinic Ga₂O₃.

In another form, the two or more epitaxial (Al_(x)Ga_(1−x))₂O₃ filmscomprise corundum type AlGaO₃.

In another form, x≤0.5 for each of the two or more epitaxial(Al_(x)Ga_(1−x))₂O₃ films.

In a fourth aspect, the present disclosure provides a method for forminga multilayer semiconducting device comprising: forming a first layerhaving a first crystal symmetry type and a first composition; anddepositing in a non-equilibrium environment a metal oxide layer having asecond crystal symmetry type and a second composition onto the firstlayer, wherein depositing the second layer onto the first layercomprises initially matching the second crystal symmetry type to thefirst crystal symmetry type.

In another form, initially matching the second crystal symmetry type tothe first crystal symmetry type comprises matching a first latticeconfiguration of the first crystal symmetry type with a second latticeconfiguration of the second crystal symmetry at a horizontal planargrowing interface.

In another form, matching the first and second crystal symmetry typescomprise substantially matching respective end plane lattice constantsof the first and second lattice configurations.

In another form, the first layer is corundum Al₂O₃ (sapphire) and themetal oxide layer is corundum Ga₂O₃.

In another form, the first layer is monoclinic Al₂O₃ and the metal oxidelayer is monoclinic Ga₂O₃.

In another form, the first layer is R-plane corundum Al₂O₃ (sapphire)prepared under O-rich growth conditions and the metal oxide layer iscorundum AlGaO₃ selectively grown at low temperatures (<550° C.).

In another form, the first layer is M-plane corundum Al₂O₃ (sapphire)and the metal oxide layer is corundum AlGaO₃.

In another form, the first layer is A-plane corundum Al₂O₃ (sapphire)and the metal oxide layer is corundum AlGaO₃.

In another form, the first layer is corundum Ga₂O₃ and the metal oxidelayer is. corundum Al₂O₃ (sapphire).

In another form, the first layer is monoclinic Ga₂O₃ and the metal oxidelayer is. monoclinic Al₂O₃ (sapphire).

In another form, the first layer is (−201)-oriented monoclinic Ga₂O₃ andthe metal oxide layer is. (−201)-oriented monoclinic AlGaO₃.

In another form, the first layer is (010)-oriented monoclinic Ga₂O₃ andthe metal oxide layer is. (010)-oriented monoclinic AlGaO₃.

In another form, the first layer is (001)-oriented monoclinic Ga₂O₃ andthe metal oxide layer is. (001)-oriented monoclinic AlGaO₃.

In another form, the first and second crystal symmetry types aredifferent, and matching the first and second lattice configurationcomprises reorienting the metal oxide layer to substantially matchingthe in-plane atomic arrangement at the horizontal planar growinginterface.

In another form, the first layer is C-plane corundum Al₂O₃ (sapphire)and wherein the metal oxide layer is any one of monoclinic, triclinic orhexagonal AlGaO₃.

In another form, the C-plane corundum Al₂O₃ (sapphire) is prepared underO-rich growth conditions to selectively grow hexagonal AlGaO₃ at lowergrowth temperatures (<650° C.).

In another form, the C-plane corundum Al₂O₃ (sapphire) is prepared underO-rich growth conditions to selectively grow monoclinic AlGaO₃ at highergrowth temperatures (>650° C.) with Al % limited to approximately45-50%.

In another form, the R-plane corundum Al₂O₃ (sapphire) is prepared underO-rich growth conditions to selectively grow monoclinic AlGaO3 at highergrowth temperatures (>700°) with Al %<50%.

In another form, the first layer is A-plane corundum Al₂O₃ (sapphire)and wherein the metal oxide layer is (110)-oriented monoclinic Ga₂O₃.

In another form, the first layer is (110)-oriented monoclinic Ga₂O₃ andwherein the metal oxide layer is corundum AlGaO₃.

In another form, the first layer is (010)-oriented monoclinic Ga₂O₃ andthe metal oxide layer is. (111)-oriented cubic MgGa₂O₄.

In another form, the first layer is (100)-oriented cubic MgO and whereinthe metal oxide layer is (100)-oriented monoclinic AlGaO₃.

In another form, the first layer is (100)-oriented cubic NiO and themetal oxide layer is (100)-oriented monoclinic AlGaO3

In another form, initially matching the second crystal symmetry type tothe first crystal symmetry type comprises depositing, in anon-equilibrium environment, a buffer layer between the first layer andthe metal oxide layer wherein a buffer layer crystal symmetry type isthe same as the first crystal symmetry type to provide atomically flatlayers for seeding the metal oxide layer having the second crystalsymmetry type.

In another form, the buffer layer comprises an O-terminated template forseeding the metal oxide layer.

In another form, the buffer layer comprises a metal terminated templatefor seeding the metal oxide layer.

In another form, the first and second crystal symmetry types areselected from the group consisting of cubic, hexagonal, orthorhombic,trigonal, rhombic and monoclinic.

In another form, the first crystal symmetry type and first compositionof the first layer and the second crystal symmetry type and secondcomposition of the second layer are selected to introduce apredetermined strain into the second layer.

In another form, the first layer is a metal oxide layer.

In another form, the first and second layers form a unit cell that isrepeated with a fixed unit cell period to form a superlattice.

In another form, the first and second layers are configured to havesubstantially equal but opposite strain to facilitate forming of thesuperlattice without defects.

In another form, the method comprises depositing, in a non-equilibriumenvironment, an additional metal oxide layer having a third crystalsymmetry type and a third composition onto the metal oxide layer.

In another form, the third crystal type is selected from the groupconsisting of cubic, hexagonal, orthorhombic, trigonal, rhombic andmonoclinic.

In another form, the multilayer semiconductor device is anoptoelectronic semiconductor device for generating light of apredetermined wavelength.

In another form, the predetermined wavelength is in the wavelength rangeof 150 nm to 700 nm.

In another form, the predetermined wavelength is in the wavelength rangeof 150 nm to 280 nm.

In a fifth aspect, the present disclosure provides a method for formingan optoelectronic semiconductor device for generating light of apredetermined wavelength, the method comprising: introducing asubstrate; depositing in a non-equilibrium environment a firstconductivity type region comprising one or more epitaxial layers ofmetal oxide; depositing in a non-equilibrium environment an opticalemission region comprising one or more epitaxial layers of metal oxideand comprising an optical emission region band structure configured forgenerating light of the predetermined wavelength; and depositing in anon-equilibrium environment a second conductivity type region comprisingone or more epitaxial layers of metal oxide

In another form, the predetermined wavelength is in the wavelength rangeof about 150 nm to about 700 nm. In another form, the predeterminedwavelength is in the wavelength range of about 150 nm to about 425 nm.In one example, bismuth oxide can be used to produce wavelengths up toapproximately 425 nm.

In another form, the predetermined wavelength is in the wavelength rangeof about 150 nm to about 280 nm.

In yet another form, the optical emission efficacy is controlled by theselection of the crystal symmetry type of the optically emissive region.The optical selection rule for electric-dipole emission is governed bythe symmetry properties of the conduction band and valence band statesas well as the crystal symmetry type. An optically emissive regionhaving crystal structure possessing point group symmetry can have aproperty of either a center-of-inversion symmetry or non-inversionsymmetry. Advantageous selection of crystal symmetry to promoteelectric-dipole or magnetic-dipole optical transitions are claimedherein for application to the optically emissive region. Conversely,advantageous selection of crystal symmetry to inhibit electric-dipole ormagnetic-dipole optical transitions are also possible for promotingoptically non-absorptive regions of the device.

By way of overview, FIG. 1 is a process flow diagram for constructing anoptoelectronic semiconductor optoelectronic device in accordance with anillustrative embodiment. In one example, the optoelectronicsemiconductor device is a UVLED and in a further example, the UVLED isconfigured to generate a predetermined wavelength in the wavelengthregion of about 150 nm to about 280 nm. In this example, theconstruction process comprises selecting initially (i) the operatingwavelength desired (e.g., a UVC wavelength or lower wavelength) in step10 and (ii) the optical configuration of the devices in step 60 (e.g., avertically emissive device 70 where the light output vector or directionis substantially perpendicular to the plane of the epi-layers, or awaveguide device 75 where the light output vector is substantiallyparallel to the plane of the epi-layers). The optical emissioncharacteristics of the device is implemented in part by selection ofsemiconductor materials 20 and optical materials 30.

Taking the example of a UVLED, the optoelectronic semiconductor deviceconstructed in accordance with the process illustrated in FIG. 1 willcomprise an optical emission region based on the selected opticalemission region material 35 wherein a photon is created by theadvantageous spatial recombination of an electron in the conduction bandand a hole in the valence band. In one example, the optical emissionregion comprises one or more metal oxide layers.

The optical emission region may be a direct bandgap type band structureconfiguration. This can be an intrinsic property of the materials(s)selected or can be tuned using one or more of the techniques of thepresent disclosure. The optical recombination or optical emission regionmay be clad by electron and hole reservoirs comprising n-type and p-typeconductivity regions. The n-type and p-type conductivity regions areselected from electron and hole injection materials 45 that may havelarger bandgaps relative to the optical emission region material 35, orcan comprise an indirect bandgap structure that limits the opticalabsorption at the operating wavelength. In one example, the n-type andp-type conductivity regions are formed of one or more metal oxidelayers.

Impurity doping of Ga₂O₃ and low Al % AlGaO₃ is possible for both n-typeand p-type materials. N-type doping is particularly favorable for Ga₂O₃and AlGaO₃, whereas p-type doping is more challenging but possible.Impurities suitable for n-type doping are Si, Ge, Sn and rare-earths(e.g., Erbium (Er) and Gadolinium (Gd)). The use of Ge-fluxes forco-deposition doping control is particularly suitable. For p-typeco-doping using group-III metals, Ga-sites can be substituted viaMagnesium (Mg²⁺), Zinc (Zn²⁺) and atomic-Nitrogen (N³⁻ substitution forO-sites). Further improvements can also be obtained using Iridium (Ir),Bismuth (Bi), Nickel (Ni) and Palladium (Pd).

Digital alloys using NiO, Bi₂O₃, Ir₂O₃ and PdO may also be used in someembodiments to advantageously aid p-type formation in Ga₂O₃-basedmaterials. While p-type doping for AlGaO₃ is possible, alternativedoping strategies are also possible using cubic crystal symmetry metaloxides (e.g. Li-doped NiO or Ni vacancy NiO_(x>1)) and wurtzite p-typeMg:GaN.

Yet a further opportunity is the ability to form highly polar forms ofhexagonal crystal symmetry and epsilon-phase Ga₂O₃ directly integratedto AlGaO₃ thereby inducing polarization doping in accordance with theprinciples and techniques described and referred to in U.S. Pat. No.9,691,938. The optical materials 30 necessary for the confinement oflight in the device as differential changes in refractive index alsorequires selection. For far or vacuum ultraviolet, the selection ofoptically transparent materials ranges from MgO to metal-fluorides, suchas MgF₂, LiF and the like. It has been found in accordance with thepresent disclosure that single crystal LiF and MgO substrates areadvantageous for the realization of UVLEDs.

The electrical materials 50 forming the contacts to the electron andhole injector regions are selected from low- and high-work functionmetals, respectively. In one example, the metal ohmic contacts areformed in-situ directly on the final metal oxide surface, as a resultreducing any mid-level traps/defects created at the semiconductingoxide-metal interface. The device is then constructed in step 80.

FIGS. 2A and 2B show schematically a vertical emission device 110 andwaveguide emissive device 140 in accordance with illustrativeembodiments. Device 110 has a substrate 105 and emission structure 135.Similarly, device 140 has a substrate 155 and emission structure 145.Light 125 and 130 from device 110 and light 150 from device 140,generated from the light generation region 120, propagates through thedevice from region 120 and is confined by a light escape cone defined bythe difference in refractive indices at the semiconductor-air interface.As metal oxide semiconductors have extremely large bandgap energy, theyhave a substantially lower refractive index compared to III-N materials.Therefore, the use of metal oxide materials provides an improved lightescape cone and therefore higher optical output coupling efficiencycompared to conventional emission devices. Waveguide devices havingsingle mode and multimode operation are also possible.

Broad area stripe waveguides can also be constructed further utilizingelemental metals Al- or Mg-metal to directly form ultraviolet plasmonguiding at the semiconductor-metal interface. This is an efficientmethod for forming waveguide structures. The E-k band structure for Al,Mg and Ni will be discussed below. Once the desired materials selectionsare available the process for constructing the semiconductoroptoelectronic device may occur at step 80 (see FIG. 1).

FIG. 3A depicts functional regions of the epitaxial structure of anoptoelectronic semiconductor device 160 for generating light of apredetermined wavelength according to an illustrative embodiment.

A substrate 170 is provided with advantageous crystal symmetry andin-plane lattice constant matching at the surface to enable homoepitaxyor heteroepitaxy of a first conductivity type region 175 with asubsequent non-absorbing spacer region 180, an optical emission region185, an optional second spacer region 190 and a second conductivity typeregion 195. In one example, the in-plane lattice constant and thelattice geometry/arrangement are matched to modify (i.e., reduce)lattice defects. Electrical excitation is provided by a source 200 thatis connected to the electron and hole injection regions of the first andsecond conductivity type regions 175 and 195. Ohmic metal contacts andlow-bandgap or semi-metallic zero-bandgap oxide semiconductors are shownin FIG. 3B as regions 196, 197, 198 in another illustrative embodiment.

First and second conductivity type regions 175 and 195 are formed in oneexample using metal oxides having wide bandgap and are electricallycontacted using ohmic contact regions 197, 198 and 196 as describedherein. In the case of an insulating type substrate 170 the electricalcontact configuration is via ohmic contact region 198 and firstconductivity type region 175 for one electrical conductivity type (viz.,electron or holes) and the other using ohmic contact region 196 andsecond conductivity type region 195. Ohmic contact region 198 mayoptionally be made to an exposed portion of first conductivity typeregion 175. As the insulating substrate 170 may further be transparentor opaque to the operating wavelength, for the case of a transparentsubstrate the lower ohmic contact region 197 may be utilized as anoptical reflector as part of an optical resonator in another embodiment.

For the case of a vertical conduction device, the substrate 170 iselectrically conducting and maybe either be transparent or opaque to theoperating wavelength. Electrical or ohmic contact regions 197 and 198are disposed to advantageously enable both electrical connection andoptical propagation within the device.

FIG. 3C illustrates schematically further possible electricalarrangements for the electrical contact regions 196 and 198 showing amesa etched portion to expose lower conductivity type regions 175 and198. The ohmic contact region 196 may further be patterned to expose aportion of the device for light extraction.

FIG. 3D shows yet a further electrical configuration wherein theinsulating substrate 170 is used such that the first conductivity typeregion 175 is exposed and an electrical contact formed on a partiallyexposed portion of first conductivity type region 175. For the case ofan electrically conductive and transparent substrate contact, ohmiccontact region 198 is not required and a spatially disposed electricalcontact region 197 is used.

FIG. 3E yet further shows a possible arrangement of an optical aperture199 etched partially or fully into an optically opaque substrate 170 forthe optical coupling of light generated from optical emission region185. The optical aperture may be utilized with the previous embodimentsof FIGS. 3A-3D as well.

FIG. 4 shows schematically operation of optoelectronic semiconductordevice 160 wherein an example configuration comprises an electroninjection region 180 and a hole injection region 190 with electricalbias 200 to transport and direct mobile electrons 230 and holes 225 intothe recombination region 220. The resulting electron and holerecombination forms a spatial optical emission region 185.

Extremely large energy bandgap (EG) metal oxide semiconductors (EG>4 eV)may exhibit low mobility hole-type carriers and may even be highlylocalized spatially—as a result limiting the spatial extent for holeinjection. The region in the vicinity of the hole injection region 190and recombination region 220 may then become advantageous forrecombination process. Furthermore, the hole injection region 190 itselfmay be the preferred region for injecting electrons such thatrecombination region 220 is located within a portion of hole injectionregion 190.

Referring now to FIG. 5, light or optical emission is generated withinthe device 160 by selective spatial recombination of electrons and holesto create high energy photons 240, 245 and 250 of a predeterminedwavelength dictated by the configuration of the band structure of themetal oxide layer or layers forming the optical emission region 185 aswill be described below. The electrons and holes are bothinstantaneously annihilated to create a photon that is a property of theband structure of the metal oxide selected.

The light generated within optical emission region 185 can propagatewithin the device according to the crystal symmetry of the metal oxidehost regions. The crystal symmetry group of the host metal oxidesemiconductor has definite energy and crystal momentum dispersion knownas the E-k configuration that characterizes the band structure ofvarious regions including the optical emission region 185. Thenon-trivial E-k dispersions are fundamentally dictated by the underlyingphysical atomic arrangements of definite crystal symmetry of the hostmedium. In general, the possible optical polarizations, optical energyemitted and optical emission oscillator strengths are directly relatedto the valence band dispersion of the host crystal. In accordance withthe present disclosure, embodiments advantageously configure the bandstructure including the valence band dispersion of selected metal oxidesemiconductors for application to optoelectronic semiconductor devices,such as for, in one example, UVLEDs.

Light 240 and 245 generated vertically requires optical selection rulesof the underlying band structure to be fulfilled. Similarly, there areoptical selection rules for generation of lateral light 250. Theseoptical selection rules can be achieved by advantageous arrangement ofthe crystal symmetry types and physical spatial orientation of thecrystal for each of the regions within the UVLED. Advantageousorientation of the constituent metal oxide crystals as a function of thegrowth direction is beneficial for optimal operation of the UVLEDs ofthe present disclosure. Furthermore, selection of the optical properties30 in the process flow diagram illustrated in FIG. 1 such as therefractive index forming the waveguide type device is indicated foroptical confinement and low loss.

FIG. 6 further shows for completeness, another embodiment comprising anoptical aperture 260 disposed within optoelectronic semiconductor device160 to enable the use of materials 195 which are opaque to the operatingwavelength to provide optical out coupling from optical emission region185.

FIG. 7 shows by way of overview, selection criteria 270 for one or moremetal oxide crystal compositions in accordance with illustrativeembodiments. First, semiconductor materials 275 are selected. Thesemiconductor materials 275 may include metal-oxide semiconductors 280,which may be one or more of binary oxides, ternary oxides or quaternaryoxides. The recombination region 220 forming the optical emission region185 of optoelectronic semiconductor device 160 (for example see FIG. 5)is selected to exhibit efficient electron-hole recombination whereas theconductivity type regions are selected for their ability to providesources of electrons and holes. Metal oxide semiconductors can also becreated selectively from a plurality of possible crystal symmetry typeseven with the same species of constituent metals. Binary metal oxides ofthe form A_(x)O_(y) comprising one metal species may be used, whereinthe metal specie (A) is combined with oxygen (O) in the relativeproportions x and y. Even with the same relative proportions x and y, aplurality of crystal structure configurations are possible having vastlydifferent crystal symmetry groups.

As will be described below, compositions Ga₂O₃ and Al₂O₃ exhibit severaladvantageous and distinct crystal symmetries (e.g., monoclinic,rhombohedral, triclinic and hexagonal) but require careful attention tothe utility of incorporating them and constructing a UVLED. Otheradvantageous metal oxide compositions, such as MgO and NiO, exhibit lessvariation in practically attainable crystal structures, namely cubiccrystals.

Addition of advantageous second dissimilar metal species (B) can alsoaugment a host binary metal oxide crystal structure to create a ternarymetal oxide of the form A_(x)B_(y)O_(n). Ternary metal oxides range fromdilute addition of B-species up to a majority relative fraction. Asdescribed below, ternary metal oxides may be adopted for theadvantageous formation of direct bandgap optically emissive structuresin various embodiments. Yet further materials can be engineeredcomprising three dissimilar cation-atom species coupled to oxygenforming a quaternary composition A_(x)B_(y)C_(z)O_(n).

In general, while a larger number (>4) of dissimilar metal atoms cantheoretically be incorporated to form complex oxide materials—they areseldom capable of producing high crystallographic quality withexceptionally distinct crystal symmetry structures. Such complex oxidesare in general polycrystalline or amorphous and therefore lack optimalutility for the applications to an optoelectronic device. As will beapparent, the present disclosure seeks in various examples substantiallysingle crystal and low defect density configurations in order to exploitthe band structure to form UVLED epitaxial formed devices. Someembodiments also include achieving desirable E-k configurations by theaddition of another dissimilar metal specie.

Selection of desired bandgap structures for each of the UVLED regions ofoptoelectronic semiconductor device 160 may also involve integration ofdissimilar crystal symmetry types. For example, a monoclinic crystalsymmetry host region and a cubic crystal symmetry host region comprisinga portion of the UVLED may be utilized. The epitaxial formationrelationships then involve attention toward the formation of low defectlayer formation. The type of layer formation steps are then classed 285as homo-symmetry and hetero-symmetry formation. To achieve the goal ofproviding the materials forming the epilayer structure, band structuremodifiers 290 can be utilized such as biaxial strain, uniaxial strainand digital alloys such as superlattice formation.

The epitaxy process 295 is then defined by the types and sequence ofmaterial composition required for deposition. The present disclosuredescribes new processes and compositions for achieving this goal.

FIG. 8 shows the epitaxy process 300 formation steps. At step 310, afilm formation substrate for supporting the optical emission region isselected with desirable properties of crystal symmetry type, and opticaland electrical characteristics. In one example, the substrate isselected to be optically transparent to the operating wavelength and acrystal symmetry compatible with the epitaxial crystal symmetry typesrequired. Even though equivalent crystal symmetry of both the substrateand epitaxial film(s) can be used there is also an optimization 315 formatching the in-plane atomic arrangements, such as in-plane latticeconstants or advantageous co-incidence of in-plane geometry ofrespective crystal planes from dissimilar crystal symmetry types.

The substrate surface has a definite 2-dimensional crystal arrangementof terminated surface atoms. In vacuum, on a prepared surface thisdiscontinuity of definite crystal structure results in a minimization ofsurface energy of the dangling bonds of the terminated atoms. Forexample, in one embodiment a metal oxide surface can be prepared as anoxygen terminated surface or in another embodiment as a metal-terminatedsurface. Metal oxide semiconductors can have complex crystal symmetry,and pure specie termination may require careful attention. For example,both Ga₂O₃ and Al₂O₃ can be O-terminated by high temperature anneal invacuum followed by sustained exposure to atomic or molecular oxygen athigh temperature.

The crystal surface orientation 320 of the substrate can also beselected to achieve selective film formation crystal symmetry type ofthe epitaxial metal oxide. For example, A-plane sapphire can be used toadvantageously select (110)-oriented alpha-phase formation high qualityepitaxial Ga₂O₃, AlGaO₃ and Al₂O₃; whereas for C-plane sapphirehexagonal and monoclinic Ga₂O₃ and AlGaO₃ films are generated. Ga₂O₃oriented surfaces are also used selectively for film formation selectionof AlGaO₃ crystal symmetry.

The growth conditions 325 are then optimized for the relativeproportions of elemental metal and activated oxygen required to achievethe desired material properties. The growth temperature also plays animportant role in determining the crystal structure symmetry typespossible. The judicious selection of the substrate surface energy viaappropriate crystal surface orientation also dictates the temperatureprocess window for the epitaxial process during which the epitaxialstructure 330 is deposited.

A materials selection database 350 for the application toward UVLEDbased optoelectronic devices is disclosed in FIG. 9. Metal oxidematerials 380 are plotted as a function of their electron affinityenergy 375 relative to vacuum. Ordered from left to right, thesemiconductor materials have increasing optical bandgap and accordinglyhave greater utility for shorter wavelength operation UVLEDs. Usinglithium fluoride (LiF) as an example in this graph, LiF has a bandgap370 (represented as the box for each material) which is the energydifference in electron volts between conduction band minimum 360 andvalence band maximum 365. The absolute energy positions represented byconduction band minimum 360 and valence band maximum 365 are plottedwith respect to the vacuum energy. While narrow bandgap material such asrare-earth nitride (RE-N), germanium (Ge), palladium-oxide (PdO) andsilicon (Si) do not offer suitable host properties for the opticalemission region, they can be used advantageously for electrical contactformation. The use of intrinsic electron affinity of given materials canbe used to form ohmic contacts and metal-insulator-semiconductorjunctions as required.

Desirable materials combinations for use as a substrate arebismuth-oxide (Bi₂O₃), nickel-oxide (NiO), germanium-oxide (GeO_(x−2)),gallium-oxide (Ga₂O₃), lithium-oxide (Li₂O), magnesium-oxide (MgO),aluminum-oxide (Al₂O₃), single crystal quartz SiO₂, and ultimatelylithium-fluoride 355 (LiF). In particular, Al₂O₃ (sapphire), Ga₂O₃, MgOand LiF are available as large high-quality single crystal substratesand may be used as substrates for UVLED type optoelectronic devices insome embodiments. Additional embodiments for substrates for UVLEDapplications also include single crystal cubic symmetry magnesiumaluminate (MgAl₂O₄) and magnesium gallate (MgGa₂O₄). In someembodiments, the ternary form of AlGaO₃ may be deployed as a bulksubstrate in monoclinic (high Ga %) and corundum (high Al %) crystalsymmetry types using large area formation methods such as Czochralski(CZ) and edge-fed growth (EFG).

Considering host metal oxide semiconductors of Ga₂O₃ and Al₂O₃, in someembodiments alloying and/or doping via elements selected from database350 are advantageous for film formation properties.

Therefore elements selected from Silicon (Si), Germanium (Ge), Er(Erbium), Gd (Gadolinium), Pd (Palladium), Bi (Bismuth), Ir (Iridium),Zn (Zinc), Ni (Nickel), Li (Lithium), Magnesium (Mg) are desirablecrystal modification specie to form ternary crystal structures or diluteadditions to the Al₂O₃, AlGaO₃ or Ga₂O₃ host crystals (seesemiconductors 280 of FIG. 7).

Further embodiments include selection of the group of crystal modifiersselected from the group of Bi, Ir, Ni, Mg, Li.

For application to the host crystals Al₂O₃, AlGaO₃ or Ga₂O₃ multivalencestates possible using Bi and Ir can be added to enable p-type impuritydoping. The addition of Ni and Mg cations can also enable p-typeimpurity substitutional doping at Ga or Al crystal sites. In oneembodiment, Lithium may be used as a crystal modifier capable ofincreasing the bandgap and modifying the crystal symmetry possible,ultimately toward orthorhombic crystal symmetry lithium gallate (LiGaO₂)and tetragonal crystal symmetry aluminum-gallate (LiAlO₂). For n-typedoping Si and Ge may be used as impurity dopants, with Ge offeringimproved growth processes for film formation.

While other materials are also possible, the database 350 providesadvantageous properties for application to UVLED.

FIG. 10 depicts a sequential epitaxial layer formation process flow 400utilized to epitaxially integrate the material regions as defined inoptoelectronic semiconductor device 160 according to an illustrativeembodiment.

A substrate 405 is prepared with surface 410 configured to accept afirst conductivity type crystal structure layer(s) 415 which maycomprise a plurality of epitaxial layers. Next first spacer regioncomposition layer(s) 420 which may comprise a plurality of epitaxiallayers is formed on layer 415. An optical emission region 425 is thenformed on layer 420, in which region 425 may comprise a plurality ofepitaxial layers. A second spacer region 430 which may comprise aplurality of epitaxial layers is then deposited on region 425. A secondconductivity type cap region 435 which may comprise a plurality ofepitaxial layers then completes a majority of the UVLED epitaxialstructure. Other layers may be added to complete the optoelectronicsemiconductor device, such as ohmic metal layers and passive opticallayers, such as for optical confinement or antireflection.

Referring to FIG. 11, a possible selection of ternary metal oxidesemiconductors 450 is shown for the cases of Gallium-Oxide-based(GaOx-based) compositions 485. Optical bandgap 480 for various values ofx in ternary oxide alloys A_(x)B_(1−x)O are graphed. As previouslystated, metal oxides may exhibit several stable forms of crystalsymmetry structure which is further complicated by the addition ofanother specie to form a ternary. However, the example general trend canbe found by selectively incorporating or alloying Aluminum, group-IIcations {Mg, Ni, Zn}, Iridium, Erbium and Gadolinium atoms, as well asLithium atoms advantageously with Ga-Oxide. Ni and Ir typically formdeep d-bands but for high Ga % can form useful optical structures. Ir iscapable of multiple valence states, where in some embodiments the Ir₂O₃form is utilized.

Alloying one of X={Ir, Ni, Zn, Bi} into Ga_(x)X_(1−x)O decreases theavailable optical bandgap (refer to curves labelled 451, 452, 453, 454).Conversely, alloying one of Y={Al, Mg, Li, RE} increases the availablebandgap of the ternary Ga_(x)Y_(1−x)O (refer to curves 456, 457, 458,459).

FIG. 11 can therefore be understood with application toward forming theoptically emissive and conductivity type regions in accordance with thepresent disclosure.

Similarly, FIG. 12 discloses a possible selection of ternary metal oxidesemiconductors 490 for the cases of Aluminum-Oxide-based (AlOx-based)compositions 485 in relation to optical bandgap 480. Scrutinizing thecurves, it can be seen that alloying one of X={Ir, Ni, Zn, Mg, Bi, Ga,RE, Li} into Al_(x)X_(1−x)O decreases the available optical bandgap. Thegroup of Y={Ni, Mg, Zn} form spinel crystal structures but all decreasesthe available bandgap of the ternary Al_(x)Y_(1−x)O (refer to curves491, 492, 493, 494, 495, 496, 500, 501). FIG. 12 also shows the energygap 502 of the alpha-phase aluminum oxide (Al₂O₃) having rhombohedralcrystal symmetry.

FIG. 12 can therefore be understood with application to forming theoptically emissive and conductivity type regions in accordance with thepresent disclosure. Shown in FIG. 28 is a chart 2800 of potentialternary oxide combinations for (0≤x≤1) that may be adopted in accordancewith the present disclosure. Chart 2800 shows the crystal growthmodifier down the left-hand column and the host crystal across the topof the chart.

FIGS. 13A and 13B are electron energy-vs-crystal momentumrepresentations of possible metal oxide based semiconductors showing adirect bandgap (FIG. 13A) and indirect bandgap (FIG. 13B) and areillustrative of concepts related to the formation of optoelectronicdevices in accordance with the present disclosure. It is known byworkers in the field of quantum mechanics and crystal structure designthat symmetry directly dictates the electronic configuration or bandstructure of a single crystal structure.

In general, for application to optically emissive crystal structures,there exists two classes of electronic band structure as shown in FIGS.13A and 13B. The fundamental process utilized in optoelectronic devicesof the present disclosure is the recombination of physical (massive)electron and hole particle-like charge carriers which are manifestationsof the allowed energy and crystal momentum. The recombination processcan occur conserving crystal momentum of the incident carriers fromtheir initial state to the final state.

To achieve a final state, wherein the electron and hole annihilate toform a massless photon (i.e., momentum k_(γ) of final state masslessphoton k_(γ)=0), requires a special E-k band structure which is shown inFIG. 13A. A metal oxide semiconductor structure having pure crystalsymmetry can be calculated using various computational techniques. Onesuch method is the Density Function Theory wherein first principles canbe used to construct an atomic structure comprising distinctionpseudopotentials attached to each constituent atom comprising thestructure. Iterative computational schemes for ab initio total-energycalculations using a plane-wave basis can be used to calculate the bandstructure due to the crystal symmetry and spatial geometry.

FIG. 13A represents the reciprocal space energy-versus-crystal momentumor band structure 520 for a crystal structure. The lowest lyingconduction band 525 having energy dispersion E_(c)({right arrow over(k)}) with respect to crystal momentum vector k={right arrow over(k)}=(k_(x)k_(y)k_(z)) describes the allowed configuration space forelectrons. The highest lying valence band 535 having energy dispersionE_(v)({right arrow over (k)}) also describes the allowed energy statesfor holes (positively charged crystal particles).

The dispersions 525 and 535 are plotted with respect to the electronenergy (increasing direction 530, decreasing direction 585) in units ofelectron volts and the crystal momentum in units of reciprocal space(positive K_(BZ) 545 and negative K_(BZ) 540 representing distinctcrystal wavevectors from the Brillouin zone center). The band structure520 is shown at the highest symmetry point of the crystal labelled asthe IF-point representing the band structure at k=0. The bandgap isdefined by the energy difference between the minima and maxima of 525and 535, respectively. An electron propagating through the crystal willminimize energy and relax to the conduction band minimum 565, similarlya hole will relax to the lowest energy state 580.

If 565 and 580 are simultaneously located at k=0 then a directrecombination process can occur wherein the electron and hole annihilateand create a new massless photon 570 with energy approximately equal tothe bandgap energy 560. That is, electron and holes at k=0 can recombineand conserve crystal moment to create a massless particle—termed a‘direct’ bandgap material. As will be disclosed, this situation is rarein practice with only a small subset of all crystal symmetry typesemiconductors exhibiting this advantageous configuration.

Referring now to crystal structure 590 of FIG. 13B, where the primarybands 525 and 620 of the band structure do not have their respectiveminima 565 and maxima 610 at k=0, this is termed an ‘indirect’configuration. The minimum bandgap energy 600 is still defined as theenergy difference between the conduction band minimum and the valenceband maximum which do occur at the same wavevector, and is known as theindirect bandgap energy 600. Optical emission processes are clearly notfavorable as crystal momentum cannot be conserved for the recombinationevent and requires secondary particles to conserve crystal momentum,such as crystal vibrational quanta phonons. In metal oxides, thelongitudinal optical phonon energy scales with bandgap and are incomparison very large to those found in for example, GaAs, Si and thelike.

It is therefore challenging to use indirect E-k configurations for thepurpose of optically emissive regions. The present disclosure describesmethods to manipulate an otherwise indirect bandgap of a specificcrystal symmetry structure and transform or modify the zone-center k=0character of the band structure into direct bandgap dispersion suitablefor optical emission. These methods are now disclosed for application tothe manufacture of optoelectronic devices and in particular to thefabrication of UVLEDs.

Even if there exists a direct bandgap configuration, the designselection is then confronted by specific crystal symmetry of given metaloxide having electric dipole selection rules governed by the symmetrycharacter group assigned to each of the energy bands. For the case ofGa₂O₃ and Al₂O₃ the optical absorption is governed between the lowestconduction band and the three topmost valence bands.

FIGS. 13C-13E show the optical emission and absorption transition at k=0with respect to a Ga₂O₃ monoclinic crystal symmetry. FIGS. 13C-13E eachshow three valence bands E_(vi)(k) 621, 622 and 623. In FIG. 13C, theoptically allowed electric dipole transition are shown for an electron566 and a hole 624 being allowed for optical polarization vectors withinthe a-axis and c-axis of the monoclinic unit cell. With respect to thereciprocal space E-k this corresponds to wave vector 627 in the Γ-Ybranches. Similarly, electric-dipole transition between electron 566 andhole 625 in FIG. 13D are allowed for polarizations along the c-axis 628of the crystal unit cell. Furthermore, higher energy transitions betweenelectron 566 and hole 626 in FIG. 13E are allowed for opticalpolarization fields along the b-axis 629 of the unit cell correspondingto the E-k (Γ-X) branch.

Clearly, the magnitude of the energy transitions 630, 631 and 632 inFIGS. 13C, 13D and 13E respectively are increasing with only the lowestenergy transition favorable for optical light emission. If, however, theFermi energy level (E_(F)) is configured such that the lowest lyingvalence band 621 is above E_(F) and 622 below E_(F), then opticalemission can occur at energy 631. These selection rules are particularlyuseful when designing waveguide devices which are optical polarizationdependent for specific TE, TM and TEM modes of operation.

By reference to the explanations above relating to band structure,referring now to FIGS. 14A-14B these diagrams show how these complexelements may be incorporated in the device structure 160. Eachfunctional region of the UVLED has a specific E-k dispersion having bothindirect and direct type materials—which can also be due to dramaticallydifferent crystal symmetry types. This then allows the opticallyemissive region to be embedded advantageously within the device.

FIGS. 14A and 14B show the representations of complex E-k materials bysingle blocks 633 defined by the layer thickness 655, 660 and 665 andthe fundamental bandgap energy 640, 645 and 650, respectively. Therelative alignments of the conduction and valence band edges are shownin blocks 633. FIG. 14B represents the electron energy 670 versus aspatial growth direction 635 for three distinct materials having bandgapenergies 640, 645 and 650. For example, a first region deposited along agrowth direction 635 using an indirect type crystal but otherwise havinga final surface lattice constant geometry capable of providingmechanical elastic deformation of the subsequent crystal 645 ispossible. For example, this can occur for the growth of AlGaO₃ directlyon Ga₂O₃.

Epitaxial Fabrication Methods

Non-equilibrium growth techniques are known in the prior art and arecalled Atomic and Molecular Beam Epitaxy, Chemical Vapor Epitaxy orPhysical Vapor Epitaxy. Atomic and Molecular Beam Epitaxy utilizesatomic beams of constituents directed toward a growth surface spatiallyseparate as shown FIG. 15. While molecular beams are also used it is thecombination of molecular and atomic beams which may be used inaccordance with the present disclosure.

One guiding principle is the use of pure constituent sources that can bemultiplexed at a growth surface through favorable condensation andkinematically favored growth conditions to physically build a crystalatomic layer by layer. While the growth crystal can be substantiallyself-assembled, the control of the present methods can also intervene atthe atomic level and deposit single specie atomic thick epilayers.Unlike equilibrium growth techniques which rely on the thermodynamicchemical potentials for bulk crystal formation, the present techniquescan deposit extraordinarily thin atomic layers at growth parameters farfrom the equilibrium growth temperature for a bulk crystal.

In one example, Al₂O₃ films are formed at film formation temperature inthe range of 300-800° C., whereas the conventional bulk equilibriumgrowth of Al₂O₃(Sapphire) is produced well in excess of 1500° C.requiring a molten reservoir containing Al and O liquid which can beconfigured to position a solid seed crystal in close proximity to themolten surface. Careful positioning of a seed crystal orientation isplaced in contact to the melt which forms a recrystallized portion inthe vicinity of the melt. Pulling the seed and partially solidifiedrecrystallized portion away from the melt forms a continuous crystalboule.

Such equilibrium growth methods for metal oxides limit the possiblecombinations of metals and the complexity of discontinuous regionspossible for heteroepitaxial formation of complex structures. Thenon-equilibrium growth techniques in accordance with the presentdisclosure can operate at growth parameters well away from the meltingpoint of the target metal oxide and can even modulate the atomic speciepresent in a single atomic layer of a unit cell of crystal along apreselected growth direction. Such non-equilibrium growth methods arenot bound by equilibrium phase diagrams. In one example, the presentmethods utilize evaporated source materials comprising the beamsimpinging upon the growth surface to be ultrapure and substantiallycharge neutral. Charged ions are in some cases created but these shouldbe minimized as best possible.

For the growth of metal oxides the constituent source beams can bealtered in a known way for their relative ratio. For example,oxygen-rich and metal-rich growth conditions can be attained by controlof the relative beam flux measured at the growth surface. While nearlyall metal oxides grow optimally for oxygen-rich growth conditions,analogous to arsenic-rich growth of gallium arsenide GaAs, somematerials are different. For example, GaN and AlN require metal richgrowth conditions with extremely narrow growth window, which are one ofthe most limiting reasons for high volume production.

While metal oxides favor oxygen-rich growth with wide growthwindows—there are opportunities to intervene and create intentionalmetal-deficient growth conditions. For example, both Ga₂O₃ and NiO favorcation vacancies for the production of active hole conductivity type. Aphysical cation vacancy can produce an electronic carrier type hole andthus favor p-type conduction.

Referring now to FIG. 41, and by way of overview, there is shown aprocess flow diagram of a method 4100 for forming an optoelectronicsemiconductor device according to the present disclosure. In one examplethe optoelectronic semiconductor device is configured to emit light inthe wavelength of about 150 nm to about 280 nm.

At step 4110 a metal oxide substrate is provided having an epitaxialgrowth surface. At step 4120, the epitaxial growth surface is oxidizedto form an activated epitaxial growth surface. At step 4130, theactivated epitaxial growth surface is exposed to one or more atomicbeams each comprising high purity metal atoms and one or more atomicbeams comprising oxygen atoms under conditions to deposit two or moreepitaxial metal oxide films or layers.

Referring again to FIG. 15 there is shown an epitaxial deposition system680 for providing Atomic and Molecular Beam Epitaxy in accordance with,in one example, method 4100 referred to in FIG. 41.

In one example, a substrate 685 rotates about an axis AX and is heatedradiatively by a heater 684 with emissivity designed to match theabsorption of a metal oxide substrate. The high vacuum chamber 682 has aplurality of elemental sources 688, 689, 690, 691, 692 capable ofproducing atomic or molecular species as beams of a pure constituent ofatoms. Also shown are plasma source or gas source 693, and gas feed 694which is a connection to gas source 693.

For example, sources 689-692 may comprise effusion type sources ofliquid Ga and Al and Ge or precursor based gases. The active oxygensources 687 and 693 may be provided via plasma excited molecular oxygen(forming atomic-O and O₂*), ozone (O₃), nitrous oxide (N₂O) and thelike. In some embodiments, plasma activated oxygen is used as acontrollable source of atomic oxygen. A plurality of gases can beinjected via sources 695, 696, 697 to provide a mixture of differentspecies for growth. For example, atomic and excited molecular nitrogenenable n-type, p-type and semi-insulating conductivity type films to becreated in GaOxide-based materials. The vacuum pump 681 maintainsvacuum, and mechanical shutters intersecting the atomic beams 686modulate the respective beam fluxes providing line of sight to thesubstrate deposition surface.

This method of deposition is found to have particular utility forenabling flexibility toward incorporating elemental species intoGa-Oxide based and Al-Oxide based materials.

FIG. 16 shows an embodiment of an epitaxial process 700 for constructingUVLEDs as a function of the growth direction 705. Homo-symmetry typelayers 735 can be formed using a native substrate 710. The substrate 710and crystal structure epitaxy layers 735 are homo-symmetrical, beinglabeled here as Type-1. For example, a corundum type sapphire substratecan be used to deposit corundum crystal symmetry type layers 715, 720,725, 730. Yet another example is the use of a monoclinic substratecrystal symmetry to form monoclinic type crystal symmetry layers715-730. This is readily possible using native substrates for growth ofthe target materials disclosed herein (e.g., see Table I of FIG. 43A).Of particular interest is the growth of epitaxial layer formations suchas corundum AlGaO₃ having a plurality of compositions of layers 715-730.Alternatively, a monoclinic Ga₂O₃ substrate 710 can be used to form aplurality of monoclinic AlGaO3 compositions of layers 715-730.

Referring now to FIG. 17, a further epitaxial process 740 is illustratedthat uses a substrate 710 with crystal symmetry that is inherentlydissimilar to the target epitaxial metal oxide epilayer crystal types oflayers 745, 750, 755, 760. That is, the substrate 710 is of crystalsymmetry Type-1 which is hetero-symmetrical to the crystal structureepitaxy 765 that is made of layers 745, 750, 755, 760 that are allType-2.

For example, C-plane corundum sapphire can be used as a substrate todeposit at least one of a monoclinic, triclinic or hexagonal AlGaO₃structure. Another example is the use of (110)-oriented monoclinic Ga₂O₃substrate to epitaxially deposit corundum AlGaO₃ structure. Yet afurther example is the use of a MgO (100) oriented cubic symmetrysubstrate to epitaxially deposit (100)-oriented monoclinic AlGaO₃ films.

Process 740 can also be used to create corundum Ga₂O₃ modified surface742 by selectively diffusing Ga-atoms into the surface structureprovided by the Al₂O₃ substrate. This can be done by elevating thegrowth temperature of the substrate 710 and exposing the Al₂O₃ surfaceto an excess of Ga while also providing an O-atom mixture. For Ga-richconditions and elevated temperatures Ga-adatoms attach selectively toO-sites and form a volatile sub-oxide Ga₂O, and further excess Gadiffuses Ga-adatoms into the Al₂O₃ surface. Under suitable conditions acorundum Ga₂O₃ surface structure results enabling lattice matching ofGa-rich AlGaO₃ corundum constructions or thicker layers can result inmonoclinic AlGaO₃ crystal symmetry.

FIG. 18 describes yet another embodiment of a process 770 wherein abuffer layer 775 is deposited on the substrate 710, the buffer layer 775having the same crystal symmetry type as substrate 710 (Type-1), therebyenabling atomically flat layers to seed alternate crystal symmetry typesof layers 780, 785, 790 (Type 2, 3 . . . N). For example, a monoclinicbuffer 775 is deposited upon a monoclinic bulk Ga₂O₃ substrate 710. Thencubic MgO and NiO layers 780-790 are formed. In this figure, thehetero-symmetrical crystal structure epitaxy with the homo-symmetricalbuffer layer is labeled as structure 800.

FIG. 19 depicts yet a further embodiment of a process 805 showingsequential variation along a growth direction 705 of a plurality ofcrystal symmetry types. For example, a corundum Al₂O₃ substrate 710(Type-1) creates an O-terminated template 810 which then seeds acorundum AlGaO₃ layer 815 of Type-2 crystal symmetry. A hexagonal AlGaO₃layer 820 of Type-3 crystal symmetry can then be formed followed bycubic crystal symmetry type (Type-N) such as a MgO or NiO layer 830. Thelayers 815, 820, 825 and 830 are collectively labeled in this figure ashetero-symmetrical crystal structure epitaxy 835. Such crystal growthmatching is possible using vastly different crystal symmetry type layersif in-plane lattice co-incidence geometry can occur. While rare, this isfound to be possible in the present disclosure with (100)-oriented cubicMg_(x)Ni_(1−x)O (0≤x≤1) and monoclinic AlGaO₃ compositions. Thisprocedure can then be repeated along a growth direction.

Yet another embodiment is shown in FIG. 20A where the substrate 710 ofType-1 crystal symmetry has a prepared surface (template 810) seeding afirst crystal symmetry type 815 (Type-2) which then can be engineered totransition to another symmetry type 845 (Transition Type 2-3) over agiven layer thickness. An optional layer 850 can then be grown with yetanother crystal symmetry type (Type-N). For example, C-plane sapphiresubstrate 710 forms a corundum Ga₂O₃ layer 815 which then relaxes to ahexagonal Ga₂O₃ crystal symmetry type or a monoclinic crystal symmetrytype. Further growth of layer 850 then can be used to form a highquality relaxed layer of high crystal structure quality. The layers 815,845 and 850 are collectively labeled in this figure ashetero-symmetrical crystal structure epitaxy 855.

Referring now to FIG. 20B, there is shown a chart 860 of the variationin a particular crystal surface energy 865 as a function of crystalsurface orientation 870 for the cases of corundum-Sapphire 880 andmonoclinic Gallia single crystal oxide materials 875. It has been foundin accordance with the present disclosure that the crystal surfaceenergy for technologically relevant corundum Al₂O₃ 880 and monoclinicsubstrates can be used to selectively form AlGaO₃ crystal symmetrytypes.

For example, Sapphire C-plane can be prepared under O-rich growthconditions to selectively grow hexagonal AlGaO₃ at lower growthtemperature (<650° C.) and monoclinic AlGaO₃ at higher temperatures(>650° C.). Monoclinic AlGaO₃ is limited to Al % of approximately 45-50%owing to the monoclinic crystal symmetry having approximately 50%tetrahedrally coordinated bonds (TCB) and 50% octahedrally coordinatedbonds (OCB). While Ga can accommodate both TCB and OCB, Al seeks inpreference the OCB sites. R-plane sapphire can accommodate corundumAlGaO₃ compositions with Al % ranging 0-100% grown at low temperaturesof less than about 550° C. under O-rich conditions and monoclinic AlGaO₃with Al<50% at elevated temperatures >700° C.

M-plane sapphire surprisingly provides yet an even more stable surfacewhich can grow exclusively corundum AlGaO₃ composition for Al %=0-100%,providing atomically flat surfaces.

Even more surprising is the discovery of A-plane sapphire surfacespresented for AlGaO₃ which are capable of extremely low defect densitycorundum AlGaO₃ compositions and superlattices (see discussion below).This result is fundamentally due to the fact that corundum Ga₂O₃ andcorundum Al₂O₃ both share exclusive crystal symmetry structure formed byOCBs. This translates into very stable growth conditions with a growthtemperature window ranging from room temperature to 800° C. This clearlyshows attention toward crystal symmetry designs that can create newstructural forms applicable to LEDs such as UVLEDs.

Similarly, native monoclinic Ga₂O₃ substrates with (−201)-orientedsurfaces can only accommodate monoclinic AlGaO₃ compositions. The Al %for (−201)-oriented films is significantly lower owing to the TCBpresented by the growing crystal surface. This does not favor large Alfractions but can be used to form extremely shallow MQWs ofAlGaO₃/Ga₂O₃.

Surprisingly the (010)- and (001)-oriented surface of monoclinic Ga₂O₃can accommodate monoclinic AlGaO₃ structures of exceedingly high crystalquality. The main limitation for AlGaO₃ Al % is the accumulation ofbiaxial strain. Careful strain management in accordance with the presentdisclosure using AlGaO₃/Ga₂O₃ superlattices also finds a limiting Al%<40%, with higher quality films achieved using (001)-oriented Ga₂O₃substrate. Yet a further example of (010)-oriented monoclinic Ga₂O₃substrates is the extremely high quality lattice matching ofMgGa₂O₄(111)-oriented films having cubic crystal symmetry structures.

Similarly, MgAl₂O₄ crystal symmetry is compatible with corundum AlGaO₃compositions. It is also found experimentally in accordance with thepresent disclosure that (100)-oriented Ga₂O₃ provides an almost perfectcoincidence lattice match for cubic MgO(100) and NiO(100) films. Evenmore surprising is the utility of (110)-oriented monoclinic Ga₂O₃substrates for the epitaxial growth of corundum AlGaO₃.

These unique properties provide for the selective utility of Al₂O₃ andGa₂O₃ crystal symmetry type substrates, as an example, with theselective use of crystal surface orientations to offer many advantagesfor the fabrication of LEDs and in particular UVLED.

In some embodiments, conventional bulk crystal growth techniques may beadopted to form corundum AlGaO₃ composition bulk substrates havingcorundum and monoclinic crystal symmetry types. These ternary AlGaO₃substrates can also prove valuable for application to UVLED devices.

Band Structure Modifiers

Optimizing the AlGaO₃ band structure can be achieved by carefulattention to the structural deformations of a given crystal symmetrytype. For application to a solid-state, and in particular asemiconductor-based electro-optically driven ultraviolet emissivedevice, the valence band structure (VBS) is of major importance. It istypically the VBS E-k dispersion which determines the efficacy for thecreation of optical radiation by direct recombination of electrons andholes. Therefore, attention is now directed toward valence band tuningoptions for achieving in one example UVLED operation.

Configuring of the Band Structure by Bi-Axial Strain

In some embodiments, selective epitaxial deposition of AlGaO₃ crystalstructures can be formed under the elastic structural deformation by theuse of composition control or by using a surface crystal geometricarrangement that can epitaxially register the AlGaO₃ film while stillmaintaining an elastic deformation of the AlGaO₃ unit cell.

For example, FIGS. 21A-21C depict the change in E-k band structure inthe vicinity of the Brillouin zone-center (k=0) which favors e-hrecombination for generating bandgap energy photons under the influenceof bi-axial strain applied to the crystal unit cell. The band structuresfor both corundum and monoclinic Al₂O₃ are direct. Depositing Al₂O₃,Ga₂O₃ or AlGaO₃ thin films onto a suitable surface which can elasticallystrain the in-plane lattice constant of the film may be achieved andengineered in accordance with the present disclosure.

The lattice constant mismatches between Al₂O₃ and Ga₂O₃ are shown inTable II of FIG. 43B. The ternary alloys can be roughly interpolatedbetween the end point binaries for the same crystal symmetry type. Ingeneral, an Al₂O₃ film deposited on a Ga₂O₃ substrate conserving crystalorientations will create the Al₂O₃ film in biaxial tension, whereas aGa₂O₃ film deposited on an Al₂O₃ substrate having the same crystalorientation will be in a state of compression.

The monoclinic and corundum crystals have non-trivial geometricstructures with relatively complex strain tensors compared toconventional cubic, zinc-blende or even wurtzite crystals. The generaltrend observed on E-k dispersion in vicinity of the BZ centre is shownin FIGS. 21A-21B. For example, diagram 890 of FIG. 21A describes ac-plane corundum crystal unit cell 894 having a strain free (σ=0) E-kdispersion, with conduction band 891 and valence band 892 separated by abandgap 893. Biaxial compression of the unit cell 899 in diagram 895 ofFIG. 21B changes the dispersion by hydrostatically lifting theconduction band, e.g., see conduction band 896 and warping the E-kcurvature of the valence band 897. The compressively strained (σ<0)bandgap 898 is generally increased E_(G) ^(σ<0)>E_(G) ^(σ=0).

Conversely, as shown in diagram 900 of FIG. 21C, biaxial tension appliedto the unit cell 904 has the effect of reducing the bandgap 903 E_(G)^(σ>0)<E_(G) ^(σ=0), lowering the conduction band 901 and flattening thevalence band curvature 902. As the valence band curvature is directlyrelated to the hole effective mass, a larger curvature decreases theeffective hole mass, whereas smaller curvature (i.e., flatter E-k bands)increase the hole effective mass (note: a totally flat valence banddispersion potentially creates immobile holes). Therefore, it ispossible to improve the Ga₂O₃ valence band dispersion by judiciouschoice of biaxial strain via the epitaxy on a suitable crystal surfacesymmetry and in-plane lattice structure.

Configuring of the Band Structure by Uni-Axial Strain

Of particular interest is the possibility of using uniaxial strain toadvantageously modify the valence band structure as shown in FIGS. 22Aand 22B, where reference numbers in FIG. 22A correspond to those of FIG.21A. For example, in-plane uniaxial deformation of the unit cell 894along substantially one crystal direction as shown in unit cell 909 willasymmetrically deform the valence band 907 as shown in diagram 905,which also shows conduction band 906 and bandgap 908.

For the case of monoclinic and corundum crystal symmetry films, similarbehavior will occur and can be shown via the growth of elasticallystrained superlattice structures comprising Al₂O₃/Ga₂O₃,Al_(x)Ga_(1−x)O₃/Ga₂O₃ and Al_(x)Ga_(1−x)O₃/Al₂O₃ on Al₂O₃ and Ga₂O₃,substrates. Such structures have been grown in relation to the presentdisclosure, and the critical layer thickness (CLT) was found to dependon the surface orientation of the substrate and be in the range of 1-2nm to about 50 nm for binary Ga₂O₃ on Sapphire. For monoclinicAl_(x)Ga_(1−x)O_(3x), x≤10% the CLT can exceed 100 nm on Ga₂O₃.

Uniaxial strain can be implemented by growth on crystal symmetry surfacewith surface geometries having asymmetric surface unit cells. This isachieved in both corundum and monoclinic crystals under various surfaceorientations as described in FIG. 20B, although other surfaceorientation and crystals are also possible, for example, MgO(100),MgAl₂O₄(100), 4H-SiC(0001), ZnO(111), Er₂O₃(222) and AlN(0002) amongothers.

FIG. 22B shows the advantageous deformation of the valence bandstructure for the case of a direct bandgap. For the case of an indirectbandgap E-k dispersion, such as, thin monolayered monoclinic Ga₂O₃, thevalence band dispersion can be tuned from an indirect to a direct bandgap as shown in FIG. 23A or 23B transitioning to FIG. 23C. Consider thestrain-free band structure 915 of FIG. 23B having conduction band 916,valence band 917, bandgap 918 and valence band maximum 919. Similarly,compressive structure 910 of FIG. 23A shows conduction band 911, valenceband 912, bandgap 913 and valence band maximum 914. Tensile structure920 of FIG. 23C shows conduction band 921, valence band 922, bandgap 923and valence band maximum 924. Detailed calculations and experimentalangle resolved photoelectron spectroscopy (ARPES) can show thatcompressive and tensile strain applied to thin films of Ga₂O₃ can warpthe valence band as shown in structures 910 and 920 for the cases ofcompressive (valence band 912) and tensile (valence band 922) uniaxialstrain applied along the b-axis or c-axis of the monoclinic Ga₂O₃ unitcell.

As shown by these figures, strain plays an important role whichtypically will require management for complex epitaxy structure. Failureto manage the strain accumulation is likely to result in relief of theelastic energy within the unit cell by the creation of dislocations andcrystallographic defects which reduce the efficiency of the UVLED.

Configuration of the Band Structure by Application of Post Growth Stress

While the above techniques involve the introduction of stresses in theform of uni-axial or bi-axial strain during forming of the layers, inother embodiments external stress may be applied following formation orgrowing of the layers or layers of metal oxide to configure the bandstructure as required. Illustrative techniques that may be adopted tointroduce these stresses are disclosed in U.S. Pat. No. 9,412,911.

Configuration of the Band Structure by Selection of Compositional Alloy

Yet another mechanism which is utilized in the present disclosure andapplied to optically emissive metal oxide based UVLEDs is the use ofcompositional alloying to form ternary crystal structures with adesirable direct bandgap. In general, two distinct binary oxide materialcompositions are shown in FIGS. 24A and 24B. Band structure 925comprises metal oxide A-O with crystal structure material 930 built frommetal atoms 928 and oxygen atoms 929 having conduction band 926, valenceband dispersion 927 and direct bandgap 931. Another binary metal oxideB—O has a crystal structure material 940 built from a different metalcation 938 of type B and oxygen atoms 939 and has an indirect bandstructure 935 with conduction band 936, bandgap 941 and valence banddispersion 937. In this example, the common anion is oxygen, and bothA-O and B—O have the same underlying crystal symmetry type.

In the case where a ternary alloy may be formed by mixing cation siteswith metal atoms A and B within an otherwise similar oxygen matrix toform (A-O)_(x)(B—O)_(1−x), this will result in an A_(x)B_(1−x)Ocomposition with the same underlying crystal symmetry. On this basis, itis then possible to form a ternary metal oxide with valence band mixingeffect as shown in FIG. 25B (Note: FIGS. 25A and 25C reproduce FIGS. 24Aand 24B). The direct valence band dispersion 927 of A-O crystalstructure material 930 alloyed with B—O crystal structure material 940having indirect valence band dispersion 937 can produce a ternarymaterial 948 that exhibits improved valence band dispersion 947, andhaving conduction band 946 and bandgap 949. That is, atomic species A ofmaterial 930 incorporated into B-sites of material 940 can augment thevalence band dispersion. Atomistic Density Functional Theorycalculations can be used to simulate this concept which will fullyaccount for the pseudopotentials of the constituent atoms, strain energyand crystal symmetry.

Accordingly, alloying corundum Al₂O₃ and Ga₂O₃ can result in a directbandgap for the band structure of the ternary metal oxide alloy and canalso improve the valence band curvature of monoclinic crystal symmetrycompositions.

Configuration of the Band Structure by Selection of Digital AlloyFabrication

While ternary alloy compositions such as AlGaO₃ are desirable, anequivalent method for creating a ternary alloy is by the use of digitalalloy formation employing superlattices (SLs) built from periodicrepetitions of at least two dissimilar materials. If the each of thelayers comprising the repeating unit cell of the SL are less than orequal to the electron de Broglie wavelength (typically about 0.1 to 10'sof nm) then the superlattice periodicity forms a ‘mini-Brillouin zone’within the crystal band structure as shown in FIG. 27A. In effect, a newperiodicity is superimposed over the inherent crystal structure by theformation of the predetermined SL structure. The SL periodicity istypically in the one-dimension of the epitaxial film formation growthdirection.

In the graph 950 of FIG. 26, consider the valence band states 953 nativeto material 955, and valence band states 954 from material 956. The E-kdispersion shows an energy gap 957 along the energy axis 951 for region958, and a first Brillouin zone edge 959 relative to k=0. Region 958 isa forbidden energy gap (ΔE) between the energy band states 953 and 954,which are the bulk-like energy bands of materials 955 and 956. Ifmaterial A and B form a superlattice 968 as shown in FIG. 27B and the SLperiod L_(SL) is selected to be a multiple (e.g., L_(SL)=2a_(AB)) of theaverage lattice constant a_(AB) of A and B, then new states 961, 962,963 and 964 are generated as shown in FIG. 27A. The superlattice energypotential therefore creates a SL band gap 967 at k=0. This effectivelyfolds the energy band 953 from the first bulk Brillouin zone edge 959 tok=0. That is, when making a superlattice using the two materials 955 and956 into ultrathin layers (thicknesses 970 and 971, respectively)forming a periodic repeating unit 969, the original bulk-like valenceband states 953 and 954 are folded into new energy band states 961, 962and 963 and 964. Stated another way, the superlattice potential createsa new energy dispersion structure comprising band states 961, 962, 963and 964. As the superlattice period imposes a new spatial potential, theBrillouin zone is contracted to wavevector 975.

This type of SL structure in FIG. 27B can be created using bi-layeredpairs comprising in different examples: Al_(x)Ga_(1−x)O/Ga₂O₃,Al_(x)Ga_(1−x)O₃/Al₂O₃. Al₂O₃/Ga₂O₃ andAl_(x)Ga_(1−x)O/Al_(y)Ga_(1−y)O₃.

The general use of SLs to configure an optoelectronic device isdisclosed in U.S. Pat. No. 10,475,956.

FIG. 27C shows the SL structure for the case of a digital binary metaloxide comprising Al₂O₃ layers 983 and Ga₂O₃ layers 984. The structure isshown in terms of electron energy 981 as a function of epitaxial growthdirection 982. The period of the SL forming the repeating unit cell 980is repeated in integer or half-integer repetitions. For example, thenumber of repetitions can vary from 3 or more periods and even up to 100or 1000 or more. The average Al % content of the equivalent digitalalloy Al_(x)Ga¹⁻O is calculated as

${x_{Al}^{SL} = \frac{L_{{Al}_{2}O_{3}}}{L_{{Al}_{2}O_{3}} + L_{{Ga}_{2}O_{3}}}},$

where L_(Al) ₂ _(O) ₃ is the layer thickness of Al₂O₃ and L_(Ga) ₂ _(O)₃ =thickness of Ga₂O₃ layer.

Yet further examples of SL structures possible are shown in FIGS.27D-27F.

The digital alloy concept can be expanded to other dissimilar crystalsymmetry types, for example cubic NiO 987 and monoclinic Ga₂O₃ 986 asshown in FIG. 27D where the digital alloy 985 simulates an equivalentternary (NiO)_(x)(Ga₂O₃)_(1−x) bulk alloy.

Yet a further example is shown in digital alloy 990 of FIG. 27E usingcubic MgO layers 991 and cubic NiO layers 992 comprising the SL. In thisexample, MgO and NiO have a very close lattice match, unlike Al₂O₃ andGa₂O₃ which are high lattice mismatched.

A four layer period SL 996 is shown in the digital alloy 995 of FIG. 27Fwhere cubic MgO and NiO with oriented growth along (100) can coincidencelattice match for (100)-oriented monoclinic Ga₂O₃. Such a SL would havean effective quaternary composition of Ga_(x)Ni_(y)Mg_(z)O_(n).

Al—Ga-Oxide Band Structures

The UVLED component regions can be selected using binary or ternaryAl_(x)Ga_(1−x)O₃ compositions either bulk-like or via digital alloyformation. Advantageous valence band tuning using bi-axial or uniaxialstrain is also possible as described above. An example process flow 1000is shown in FIG. 29 describing the possible selection criteria forselecting at least one of the crystal modification methods to form thebandgap regions of the UVLED.

At step 1005, the configuration of the band structure is selectedincluding, but not limited to, band structure characteristics such aswhether the band gap is direct or indirect, band gap energy, E_(fermi),carrier mobility, and doping and polarization. At step 1010, it isdetermined whether a binary oxide may be suitable and further whetherthat band structure of the binary oxide may be modified (i.e., tuned) atstep 1015 to meet requirements. If the binary oxide material meets therequirements then this material is selected for the relevant layer atstep 1045 in the optoelectronic device. If a binary oxide is notsuitable, then it is determined whether a ternary oxide may be suitableat step 1025 and further whether the band structure of the ternary oxidemay be modified at step 1030 to meet requirements. If the ternary oxidemeets requirements then this material is selected for the relevant layerat step 1045.

If a ternary oxide is not suitable, then it is determined whether adigital alloy may be suitable at step 1035 and further whether the bandstructure of the digital alloy may be modified at step 1040 to meetrequirements. If the digital alloy meets requirements then this materialis selected for the relevant layer at step 1045. Following determinationof the layers by this method, then the optoelectronic device stack isfabricated at step 1048.

An embodiment of an energy band lineup for Al₂O₃ and Ga₂O₃ with respectto the ternary alloy Al_(x)Ga_(1−x)O₃ is shown in diagram 1050 of FIG.30 and varies in conduction and valence band offsets for corundum andmonoclinic crystal symmetry. In diagram 1050 the y-axis is electronenergy 1051 and the x-axis is different material types 1053 (Al₂O₃ 1054,(Ga₁Al₁)O₃ 1055 and Ga₂O₃ 1056). Corundum and monoclinic heterojunctionsboth appear to have type-I and type-II offsets whereas FIG. 30 simplyplots the band alignment using existing values for the electron affinityof each material.

The theoretical electronic band structures of corundum and monoclinicbulk crystal forms of Al₂O₃ and Ga₂O₃ are known in the prior art. Theapplication of strain to thin epitaxial films is however unexplored andis a subject of the present disclosure. By way of reference to the bulkband structures of Ga₂O₃ 1056 and Al₂O₃ 1054, embodiments of the presentdisclosure utilize how strain engineering can be applied advantageouslyfor the application to UVLEDs. Incorporation of the monoclinic andtrigonal strain tensor into a k.p-like Hamiltonian is necessary forunderstanding how the valence band is affected. Prior-art k.p crystalmodels as applied to zinc-blende and wurtzite crystal symmetry systemslack maturity for simulation of both the monoclinic and trigonalsystems. Current efforts are being directed to perform a calculation ofin the quadratic approximation to a valence band Hamiltonian at thecenter of the Brillioun zone of materials where this center possess thesymmetry of the point group C2_(h).

Single Crystal Aluminum-Oxide

The two main crystal forms of monoclinic (C2/m) and corundum (R3c)crystal symmetry is discussed herein for both Al₂O₃ and Ga₂O₃; however,other crystal symmetry types are also possible such as triclinic andhexagonal forms. The other crystal symmetry forms can also be applied inaccordance with the principles set out in the present disclosure.

(a) Corundum Symmetry Al₂O₃

The crystal structure of trigonal Al₂O₃ (corundum) 1060 is shown in FIG.31. The larger spheres represent Al-atoms 1064 and the smaller spheresare oxygen 1063. The unit cell 1062 has crystal axes 1061. Along thec-axis there are layers of Al atoms and O atoms. This crystal structurehas a computed band structure 1065 as shown in FIGS. 32A-32B. Theelectron energy 1066 is plotted as a function of the crystal wavevectors 1067 within the Brillouin zone. The high symmetry points withinthe Brillouin zone are labelled as shown in the vicinity of the zonecenter k=0 which is applicable to understand the optical emissionproperties of the material.

The direct bandgap has valence band maximum 1068 and conduction bandminimum 1069 at k=0. A detailed picture of the valence band in FIG. 32Bshows a complex dispersion for the two uppermost valence bands. Thetopmost valence band determines the optical emission character ifelectrons and holes are indeed capable of being injected simultaneouslyinto the Al₂O₃ band structure.

(b) Monoclinic Symmetry Al₂O₃

The crystal structure 1070 of monoclinic Al₂O₃ is shown in FIG. 33. Thelarger spheres represent Al-atoms 1064 and the smaller spheres areoxygen 1063. The unit cell 1072 has crystal axes 1071. This crystalstructure has a computed band structure 1075 as shown in FIGS. 34A-34B,where FIG. 34B is a detailed picture of the valence band. FIG. 34A alsoshows conduction band 1076. The high symmetry points within theBrillouin zone are labelled as shown in the vicinity of the zone centerk=0 which is applicable for understanding the optical emissionproperties of the material.

The monoclinic crystal structure 1070 is relatively more complex thanthe trigonal crystal symmetry and has lower density and smaller bandgapthan the corundum Sapphire 1060 form illustrated in FIG. 31.

The monoclinic Al₂O₃ form also has a direct bandgap with clear split-offhighest valence band 1077 which has lower curvature with respect to theE-k dispersion along the G-X and G-N wave vectors. The monoclinicbandgap is ˜1.4 eV smaller than the corundum form. The second highestvalence band 1078 is symmetry split from the upper most valence band.

Single Crystal Gallium-Oxide

(a) Corundum Symmetry Ga₂O₃

The crystal structure of trigonal Ga₂O₃ (corundum) 1080 is shown in FIG.35. The larger spheres represent Ga-atoms 1084 and the smaller spheresare oxygen 1083. The unit cell 1082 has crystal axes 1081. The corundum(trigonal crystal symmetry type) is also known as the alpha-phase. Thecrystal structure is identical to Sapphire 1060 of FIG. 31 with latticeconstants defining the unit cell 1082 shown in Table II of FIG. 43B. TheGa₂O₃ unit cell 1082 is larger than Al₂O₃. The corundum crystal hasoctahedrally bonded Ga-atoms.

The calculated band structure 1085 for corundum Ga₂O₃ is shown in FIGS.36A and 36B which is pseudo-direct having only a very small energydifference between the valence band maximum and the zone center k=0.Conduction band 1086 is also shown in FIG. 36A.

Biaxial and uniaxial strain when applied to corundum Ga₂O₃ using themethods described above may then be used to modify the band structureand valence band into a direct bandgap. Indeed it is possible to usetensile strain applied along the b- and/or c-axes crystal to shift thevalence band maximum to the zone center. It is estimated that −5%tensile strain can be accommodated within a thin Ga₂O₃ layer comprisingan Al₂O₃/Ga₂O₃ SL.

(b) Monoclinic Symmetry Ga₂O₃

The crystal structure of monoclinic Ga₂O₃ (corundum) 1090 is shown inFIG. 37. The larger spheres represent Ga-atoms 1084 and the smallerspheres are oxygen 1083. The unit cell 1092 has crystal axes 1091. Thiscrystal structure has a computed band structure 1095 as shown in FIGS.38A-38B. The high symmetry points within the Brillouin zone are labelledas shown in the vicinity of the zone center k=0 which is applicable forunderstanding the optical emission properties of the material.Conduction band 1096 is also shown in FIG. 38A.

Monoclinic Ga₂O₃ has an uppermost valence 1097 with a relatively flatE-k dispersion. Close inspection reveals a few eV (less than the thermalenergy k_(B)T˜25 meV) variation in the actual maximum position of thevalence band. The relatively small valence dispersion provides insightto the fact that monoclinic Ga₂O₃ will have relatively large holeeffective masses and will therefore be relatively localized withpotentially low mobility. Thus, strain can be used advantageously toimprove the band structure and in particular the valence banddispersion.

Ternary Aluminum-Gallium-Oxide

Yet another example of the unique properties of the AlGaO₃ materialssystem is demonstrated by the crystal structures 1100 as shown in FIG.39, having crystal axes 1101 and unit cell 1102. The ternary alloycomprises a 50% Al composition.

(Al_(x)Ga_(1−x))₂O₃, where x=0.5 and can be deformed into substantiallydifferent crystal symmetry form having rhombic structure. The Ga atoms1084 and Al atoms 1064 are disposed within the crystal as shown withoxygen atoms 1083. Of particular interest is the layered structure of Aland Ga atom planes. This type of structure can also be built usingatomic layer techniques to form an ordered alloy as described throughoutthis disclosure.

The calculated band structure of 1105 is shown in FIG. 40. Theconduction band minimum 1106 and valence band maximum 1107 exhibits adirect bandgap.

Ordered Ternary AlGaO₃ Alloy

Using atomic layer epitaxy methods further enables new types of crystalsymmetry structures to be formed. For example, some embodiments includeultrathin epilayers comprising alternate sequences along a growthdirection of the form of [Al—O—Ga—O—Al— . . . ]. Structure 1110 of FIG.42 shows one possible extreme case of creating ordered ternary alloysusing alternate sequences 1115 and 1120. It has been demonstrated inrelation to the present disclosure that growth conditions can be createdwhere self-ordering of Al and Ga can occur. This condition can occureven under coincident Al and Ga fluxes simultaneously applied to thegrowing surface resulting in a self-assembled ordered alloy.Alternatively, a predetermined modulation of the Al and Ga fluxesarriving at the epilayer surface can also create an ordered alloysstructure.

The ability to configure the band structure for optoelectronic devices,and in particular UVLEDS, by selecting from bulk-like metal oxides,ternary compositions or further still digital alloys are allcontemplated to be within the scope of the present disclosure.

Yet another example is the use of biaxial and uniaxial strain to modifythe band structure, with one example being the use of the(Al_(x)Ga_(1−x))₂O₃ material system employing strained layer epitaxy onAl₂O₃ or Ga₂O₃ substrates.

Substrate Selection for AlGaO-Based UVLEDs

The selection of a native metal oxide substrate is one advantage of thepresent disclosure applied to the epitaxy of the (Al_(x)Ga_(1−x))₂O₃material systems using strained layer epitaxy on Al₂O₃ or Ga₂O₃substrates.

Example substrates are listed in Table I in FIG. 43A. In someembodiments, intermediate AlGaO₃ bulk substrates may also be utilizedand are advantageous for application to UVLEDs.

A beneficial utility for monoclinic Ga₂O₃ bulk substrates is the abilityto form monoclinic (Al_(x)Ga_(1−x))₂O₃ structures having high Ga %(e.g., approximately 30-40%), limited by strain accumulation. Thisenables vertical devices due to the ability of having an electricallyconductive substrate. Conversely, the use of corundum Al₂O₃ substratesenable corundum epitaxial films (Al_(x)Ga_(1−x))₂O₃ with 0≤x≤1.

Other substrates such as MgO(100), MgAl₂O₄ and MgGa₂O₄ are alsofavorable for the epitaxial growth of metal oxide UVLED structures.

Selection and Action of Crystal Growth Modifiers

Examples of metal oxide structures are now discussed for optoelectronicapplications and in particular to the fabrication of UVLEDs. Thestructures disclosed in FIGS. 44A-44Z, which shall be describedsubsequently, are not limiting as the possible crystal structuremodifiers may be selected from either elemental cation and anionconstituents into a given metal oxide M-O (where M=Al, Ga), such asbinary Ga₂O₃, ternary (Al_(x)Ga_(1−x))₂O₃ and binary Al₂O₃.

It is found both theoretically and experimentally in accordance with thepresent disclosure that the cation specie crystal modifiers into M-Odefined above may be selected from at least one of the following:

Germanium (Ge)

Ge is beneficially supplied as pure elemental species to incorporate viaco-deposition of M-O species during non-equilibrium crystal formationprocess. In some embodiments, elemental pure ballistic beams of atomicGa and Ge are co-deposited along with an active Oxygen beam impingingupon the growth surface. For example, Ge has a valence of +4 and can beintroduced in dilute atomic ratio by substitution onto metal cationM-sites of the M-O host crystal to form stoichiometric composition ofthe form(Ge⁺⁴O₂)_(m)(Ga₂O₃)_(n)=(Ge⁺⁴O₂)_(m(m+n))(Ga₂O₃)_(n(m+n))=(Ge⁺⁴O₂)_(x)(Ga₂O₃)_(1−x)=Ge_(x)Ga_(2(1−x))O_(3−x),wherein for dilute Ge compositions x<0.1.

In accordance with the present disclosure, it was found that for Gex≤0.1, a dilute ratio of Ge provides sufficient electronic modificationto the intrinsic M-O for manipulating the Fermi-energy (E_(F)), therebyincreasing the available electron free carrier concentration andaltering the crystal lattice structure to impart advantageous strainduring epitaxial growth. For dilute compositions the host M-O physicalunit cell is substantially unperturbed. Further increase in Geconcentration results in modification of the host Ga₂O₃ crystalstructure through lattice dilation or even resulting in a new materialcomposition.

For example, for Ge x≤⅓ a monoclinic crystal structure of the host Ga₂O₃unit cell can be maintained. For example, x=0.25 forming monoclinicGe_(0.25)Ga_(1.50)O_(2.75)=Ge₁Ga₆O₁₁ is possible. Advantageously,monoclinic Ge_(x)Ga_(2(1−x))O_(3−x) (x=⅓) crystal exhibits an excellentdirect bandgap in excess of 5 eV. The lattice deformation by introducingGe increases the monoclinic unit cell preferentially along the b-axisand c-axis while retaining the a-axis lattice constant in comparison tostrain-free monoclinic Ga₂O₃.

The lattice constants for monoclinic Ga₂O₃ are (a=3.08 A, b=5.88 A,c=6.41 A) and for monoclinic Ge₁Ga₆O₁₁ (a=3.04 A, b=6.38 A, c=7.97 A).Therefore, introducing Ge creates biaxial expansion of the free-standingunit cell along the b- and c-axes. Therefore, ifGe_(x)Ga_(2(1−x))O_(3−x) is epitaxially deposited upon a bulk-likemonoclinic Ga₂O₃ surface oriented along the b- and c-axis (that is,deposited along the a-axis), then a thin film ofGe_(x)Ga_(2(1−x))O_(3−x) can be elastically deformed to induce biaxialcompression, and therefore warp the valence band E-k dispersionadvantageously, as discussed herein.

Beyond x>⅓ the higher Ge % transforms the crystal structure to cubic,for example, GeGa₂O₅.

In some embodiments, incorporation of Ge into Al₂O₃ and(Al_(x)Ga_(1−x))₂O₃ are also possible.

For example, a direct bandgap Ge_(x)Al_(2(1−x))O_(3−x) ternary can alsobe epitaxially formed by co-deposition of elemental Al and Ge and activeOxygen so as to form a thin film of monoclinic crystal symmetry. Inaccordance with the present disclosure it was found that the monoclinicstructure is stabilized for Ge % x˜0.6 creating a free-standing latticethat has a large relative expansion along the a-axis and along thec-axis, while moderate decrease along the b-axis when compared tomonoclinic Al₂O₃.

The lattice constants for monoclinic Ge₂Al₂O₇ are (a=5.34 A, b=5.34 A,c=9.81 A) and for monoclinic Al₂O₃ (a=2.94 A, b=5.671 A, c=6.14 A).Therefore, Ge_(x)Al_(2(1−x))O₃ deposited along a growth directionoriented along the b-axis and deposited further on a monoclinic Al₂O₃surface, for sufficiently thin films to maintain elastic deformation,will undergo biaxial tension.

Silicon (Si)

Elemental Si may also be supplied as a pure elemental species toincorporate via co-deposition of M-O species during non-equilibriumcrystal formation process. In some embodiments, elemental pure ballisticbeams of atomic Ga and Si are co-deposited along with an active Oxygenbeam impinging upon the growth surface. For example, Si has a valence of+4 and can be introduced in dilute atomic ratio by substitution ontometal cation M-sites of the M-O host crystal to form stoichiometriccomposition of the form(Si⁺⁴O₂)_(m)(Ga₂O₃)_(n)═(Si⁺⁴O₂)_(m/(m+n))(Ga₂O₃)n/(m+n)=(Si⁺⁴O₂)_(x)(Ga₂O₃)_(1−x)═Si_(x)Ga_(2(1−x))O_(3−x),wherein for dilute Si compositions x<0.1.

In accordance with the present disclosure, it was found that for Six≤0.1, a dilute ratio of Si provides sufficient electronic modificationto the intrinsic M-O for manipulating the Fermi-energy (E_(F)), therebyincreasing the available electron free carrier concentration andaltering the crystal lattice structure to impart advantageous strainduring epitaxial growth. For dilute compositions the host M-O physicalunit cell is substantially unperturbed. Further increase in Siconcentration results in modification of the host Ga₂O₃ crystalstructure through lattice dilation or even resulting in a new materialcomposition.

For example, for Si x≤⅓ a monoclinic crystal structure of the host Ga₂O₃unit cell can be maintained. For example, for the case of Si % x=0.25,forming monoclinic Si_(0.25)Ga_(1.50)O_(2.75)=Si₁Ga₆O₁₁ is possible. Thelattice deformation by introducing Si increases the monoclinic unit cellpreferentially along the b-axis and c-axis while retaining the a-axislattice constant in comparison to strain-free monoclinic Ga₂O₃. Thelattice constants for monoclinic Si₁Ga₆O₁₁ are (a=6.40 A, b=6.40 A,c=9.40 A) compared to monoclinic Ga₂O₃ (a=3.08 A, b=5.88 A, c=6.41 A).

Therefore, introducing Si creates biaxial expansion of the free-standingunit cell along all the a-, b- and c-axes. Therefore, ifSi_(x)Ga_(2(1−x))O_(3−x) is epitaxially deposited upon a bulk-likemonoclinic Ga₂O₃ surface oriented along the b- and c-axis (that is,deposited along the a-axis), then a thin film ofSi_(x)Ga_(2(1−x))O_(3−x) can be elastically deformed to induceasymmetric biaxial compression, and therefore warp the valence band E-kdispersion advantageously, as discussed herein.

Beyond x>⅓ the higher Si % transforms the crystal structure to cubic,for example, SiGa₂O₅.

In some embodiments, incorporation of Si into Al₂O₃ and(Al_(x)Ga_(1−x))₂O₃ are also possible. For example, orthorhombic(Si⁺⁴O₂)_(x)(Al₂O₃)_(1−x)═Si_(x)Al_(2(1−x))O_(3−x) is possible by directco-deposition of elemental Si and Al with an active Oxygen flux onto adeposition surface. If the deposition surface is selected from theavailable trigonal alpha-Al₂O₃ surfaces (e.g., A-, R-, M-plane) then itis possible to form orthorhombic crystal symmetry Al₂SiO₅ (i.e., x=0.5)which reports a large direct bandgap at the Brillouin-zone center. Thelattice constants for orthorhombic are (a=5.61 A, b=7.88 A, c=7.80 A)and trigonal (R3c) Al₂O₃(a=4.75 A, b=4.75 A, c=12.982 A).

Deposition of oriented Al₂SiO₅ films on Al₂O₃ can therefore result inlarge biaxial compression for elastically strained films. Exceeding theelastic energy limit creates deleterious crystalline misfit dislocationsand is generally to be avoided. To achieve elastically deformed film onAl₂O₃, in particular, films of thickness less than about 10 nm arepreferred.

Magnesium (Mg)

Some embodiments include the incorporation of Mg elemental species withGa₂O₃ and Al₂O₃ host crystals, where Mg is selected as a preferredgroup-II metal specie. Furthermore, incorporation of Mg into(Al_(x)Ga_(1−x))₂O₃ up to and including the formation of a quaternaryMg_(x)(Al_(x)Ga)_(y)O_(z) may also be utilized. Particular usefulcompositions of Mg_(x)Ga_(2(1−x))O_(3−2x), wherein x≤0.1, enable theelectronic structure of the Ga₂O₃ and Al_(x)Ga_(1−x))₂O₃ host to be madep-type conductivity type by substituting Ga³⁺ cation sites by Mg²⁺cations. For Al_(y)Ga_(1−y))₂O₃ y=0.3 the bandgap is about 6.0 eV, andMg can be incorporated up to about y˜0.05 to 0.1 enabling theconductivity type of the host to be varied from intrinsic weak excesselectron n-type to excess hole p-type.

Ternary compounds of the type Mg_(x)Ga_(2(1−x))O_(3−2x) andMg_(x)Al_(2(1−x))O_(3−2x) and (Ni_(x)Mg_(1−x))O are also exampleembodiments of active region materials for optically emissive UVLEDs.

In some embodiments, both stoichiometric compositions ofMg_(x)Ga_(2(1−x))O_(3−2x) and Mg_(x)Al_(2(1−x))O_(3−2x) wherein x=0.5producing cubic crystal symmetry structure exhibit advantageous directbandgap E-k dispersion are suitable for optically emissive region.

Furthermore, in accordance with the present disclosure it was found thatthe Mg_(x)Ga_(2(1−x))O_(3−2x) and Mg_(x)Al_(2(1−x))O_(3−2x) compositionsare epitaxially compatible with cubic MgO and monoclinic, corundum andhexagonal crystal symmetry forms of Ga₂O₃.

Using non-equilibrium growth techniques enables a large miscibilityrange of Mg within both Ga₂O₃ and Al₂O₃ hosts spanning MgO to therespective M-O binary. This is in contradistinction with equilibriumgrowth techniques such as CZ wherein phase separation occurs due to thevolatile Mg specie.

For example, the lattice constants of cubic and monoclinic forms ofMg_(x)Ga_(2(1−x))O_(3−2x) for x˜0.5 are (a=b=c=8.46 A) and (a=10.25 A,b=5.98, c=14.50 A), respectively. In accordance with the presentdisclosure, it was found that the cubic Mg_(x)Ga_(2(1−x))O_(3−2x) formcan orient as a thin film having (100)- and (111)-oriented films onmonoclinic Ga₂O₃(100) and Ga₂O₃(001) substrates. Also,Mg_(x)Ga_(2(1−x))O_(3−2x) thin epitaxial films can be deposited upon MgOsubstrates. Furthermore, Mg_(x)Ga_(2(1−x))O_(3−2x) 0≤x≤1 films can bedeposited directly onto MgAl₂O₄(100) spinel crystal symmetry substrates.

In further embodiments, both Mg_(x)Al_(2(1−x))O_(3−2x) andMg_(x)Ga_(2(1−x))O_(3−2x) high quality (i.e., low defect density)epitaxial films can be deposited directly onto Lithium Fluoride (LiF)substrates.

Zinc (Zn)

Some embodiments include incorporation of Zn elemental species intoGa₂O₃ and Al₂O₃ host crystals, where Zn is another preferred group-IImetal specie. Furthermore, incorporation of Zn into (Al_(x)Ga_(1−x))₂O₃up to and including the formation of a quaternaryZn_(x)(Al_(x)Ga)_(y)O_(z) may also be utilized.

Yet further quaternary compositions advantageous for tuning the directbandgap structure are the compounds of the most general form:

(Mg_(x)Zn_(1−x))_(z)(Al_(y)Ga_(1−y))_(2(1−z))O_(3−2z), where 0≤x,y,z≤1.

In accordance with the present disclosure, it was found that the cubiccrystal symmetry composition forms of z˜0.5 can be used advantageouslyfor a given fixed y composition between Al and Ga. By varying the Mg toZn ratio x, the direct bandgap can be tuned from about 4 eV≤E_(G)(x)<7eV. This can be achieved by disposing advantageously separatelycontrollable fluxes of pure elemental beams of Al, Ga, Mg and Zn andproviding an activated Oxygen flux for the anions species. In general,an excess of atomic oxygen is desired with respect to the totalimpinging metal flux. Control of the Al:Ga flux ratio and Mg:Zn ratioarriving at the growth surface can then be used to preselect thecomposition desired for bandgap tuning the UVLED regions.

Surprisingly, while Zinc-Oxide (ZnO) is generally a wurtzite hexagonalcrystal symmetry structure, when introduced into(Mg_(x)Zn_(1−x))_(z)(Al_(y)Ga_(1−y))_(2(1−z))O_(3−2z), cubic and spinelcrystal symmetry forms are readily possible using non-equilibrium growthmethods described herein. The bandgap character at the Brillouin-zonecenter can be tuned by alloy composition (x, y, z) ranging from indirectto direct character. This is advantageous for application tosubstantially non-absorbing electrical injection regions and opticalemissive regions, respectively. Furthermore, bandgap modulation ispossible for bandgap engineered structures, such as superlattices andquantum wells described herein.

Nickel (Ni)

The incorporation of Ni elemental species into Ga₂O₃ and Al₂O₃ hostcrystals is yet another preferred group-II metal specie. Furthermore,incorporation of Ni into (Al_(x)Ga_(1−x))₂O₃ up to and including theformation of a quaternary Ni_(x)(Al_(x)Ga)_(y)O_(z) may be utilized.

Yet further quaternary compositions advantageous for tuning the directbandgap structure are the compounds of the most general form:

(Mg_(x)Ni_(1−x))_(z)(Al_(y)Ga_(1−y))_(2(1−z))O_(3−2z), where 0≤x,y,z≤1.

In accordance with the present disclosure, it was discovered that thecubic crystal symmetry composition forms of z˜0.5 can be usedadvantageously for a given fixed y composition between Al and Ga. Byvarying the Mg to Ni ratio x, the direct bandgap can be tuned from about4.9 eV≤E_(G)(x)<7 eV. This can be achieved by disposing advantageouslyseparately controllable fluxes of pure elemental beams of Al, Ga<Mg andNi and providing an activated oxygen flux for the anion species. Controlof the Al:Ga flux ratio and Mg:Ni ratio arriving at the growth surfacecan then be used to preselect the composition desired for bandgap tuningthe UVLED regions.

Of enormous utility herein is the specific band structure and intrinsicconductivity type of cubic NiO. Nickel-Oxide (NiO) exhibits a nativep-type conductivity type due to the Ni d-orbital electrons. The generalcubic crystal symmetry form(Mg_(x)Ni_(1−x)z)(Al_(y)Ga_(1−y))_(2(1−z))O_(3−2z) are possible usingnon-equilibrium growth methods described herein.

Both Ni_(z)Ga_(2(1−z))O_(3−2z) and Ni_(z)Al_(2(1−z))O_(3−2z) areadvantageous for application to UVLED formation. Dilute composition ofz<0.1 was found in accordance with the present disclosure to beadvantageous for p-type conductivity creation, and for z˜0.5 the ternarycubic crystal symmetry compounds also exhibit direct bandgap at theBrillouin-zone center.

Lanthanides

There exists a large selection of the Lanthanide-metal atomic speciesavailable which can be incorporated into the binary Ga₂O₃, ternary(Al_(x)Ga_(1−x))₂O₃ and binary Al₂O₃. The Lanthanide group metals rangefrom the 15 elements starting with Lanthanum (Z=57) to Lutetium (Z=71).In some embodiments, Gadolinium Gd(Z=64) and Erbium Er(Z=68) areutilized for their distinct 4f-shell configuration and ability to formadvantageous ternary compounds with Ga₂O₃, GaAlO₃ and Al₂O₃. Again,dilute impurity incorporation of exclusively one specie selected fromRE={Gd or Er} incorporated into cation sites of (RE_(x)Ga_(1−x))₂O₃,(RE_(x)Ga_(y)Al_(1−x−y))₂O₃ and (RE_(x)Al_(1−x))₂O₃ where 0≤x, y, z≤1enable tuning of the Fermi energy to form n-type conductivity typematerial exhibiting corundum, hexagonal and monoclinic crystal symmetry.The inner 4f-shell orbitals of Gd provide opportunity for the electronicbonding to circumvent parasitic optical 4f-to-4f energy level absorptionfor wavelengths below 250 nm.

Surprisingly, it was found both theoretically and experimentally inaccordance with the present disclosure that ternary compounds of(Er_(x)Ga_(1−x))₂O₃, and (Er_(x)Al_(1−x))₂O₃ for the case of x˜0.5exhibit cubic crystal symmetry structures with direct bandgaps. It isknown to have a bixbyite crystal symmetry for binary Erbium-Oxide Er₂O₃which can be formed epitaxially as single crystal films on Si(111)substrates. However, the lattice constant available by bixbyite Er₂O₃ isnot readily applicable for seeding epitaxial films of Ga₂O₃, GaAlO₃ andAl₂O₃. In accordance with the present disclosure, it was discovered thatgraded composition incorporation along a growth direction of Erincreasing from 0 to 0.5 is necessary for creating the necessary finalsurface commensurate for epitaxy of monoclinic Ga₂O₃. Cubic crystalsymmetry forms of (Er_(x)Ga_(1−x))₂O₃, 0≤x≤0.5 may be utilized, such ascompositions exhibiting direct bandgap.

Of particular interest is the orthorhombic ternary composition of(Er_(x)Al_(1−x))₂O₃ with x˜0.5 having lattice constants (a=5.18 A,b=5.38 A, c=7.41) and exhibiting a well-defined direct energy bandgap ofE_(G)(k=0) of approximately 6.5 to 7 eV. Such a structure can bedeposited on monoclinic Ga₂O₃ and corundum Al₂O₃ substrates orepilayers. As mentioned, the inner Er³⁺ 4f-4f transitions are notpresented in the E-k band structure and are therefore classed asnon-parasitic absorption for the application of UVLEDs.

Bismuth (Bi)

Bismuth is a known specie which acts as a surfactant for GaNnon-equilibrium epitaxy of thin Gallium-Nitride GaN films. Surfactantslower the surface energy for an epitaxial film formation but in generalare not incorporated within the growing film. Incorporation of Bi evenin Gallium Arsenide is low. Bismuth is a volatile specie having highvapor pressure at low growth temperatures and would appear to be a pooradatom for incorporation into a growing epitaxial film. Surprisinglyhowever, the incorporation of Bi into Ga₂O₃, (Ga, Al)O₃ and Al₂O₃ atdilute levels x≤0.1 is extremely efficient using the non-equilibriumgrowth methods described in the present disclosure. For example,elemental sources of Bi, Ga and Al can be co-deposited with anoverpressure ratio of activated Oxygen (namely, atomic Oxygen, Ozone andNitrous Oxide). It was found in accordance with the present disclosurethat Bi incorporation in the monoclinic and corundum crystal symmetryGa₂O₃ and (Ga_(x),Al_(1−x))₂O₃ for x<0.5 exhibits a conductivity typecharacter that creates an activated hole carrier concentration suitableas a p-type conductivity region for UVLED function.

Yet higher Bi atomic incorporation x>0.1 enables band structure tuningof (Bi_(x)Ga_(1−x))₂O₃ and (Bi_(x)Al_(1−x))₂O₃ ternary compositions andindeed all the way to stoichiometric binary Bismuth Oxide Bi₂O₃.Monoclinic Bi₂O₃ forms lattice constants of (a=12.55 A, b=5.28 andc=5.67 A) which is commensurate with strained layer film growth directlyon monoclinic Ga₂O₃.

Furthermore, orthorhombic and trigonal forms may be utilized in someembodiments, exhibiting native p-type conductivity character andindirect bandgap.

Particular interest is toward the orthorhombic crystal symmetrycomposition of (Bi_(x)Al_(1−x))₂O₃ where for the case of x=⅓ exhibits anE-k dispersion that is direct and having E_(G)=4.78-4.8 eV.

Palladium (Pd)

The addition of Pd to Ga2O₃, (Ga, Al)O₃ and Al₂O₃ may be utilized insome embodiments to create metallic behavior and is applicable for theformation of ohmic contacts. In some embodiments, Palladium Oxide PdOcan be used as an in-situ deposited semi-metallic ohmic contact forn-type wide bandgap metal oxide owing to the intrinsically low workfunction of the compound (refer to FIG. 9).

Iridium (Ir)

Iridium is a preferred Platinum-group metal for incorporation intoGa₂O₃, (Ga, Al)O₃ and Al₂O₃. It was found in accordance with the presentdisclosure that Ir may bond in a large variety of valence states. Ingeneral, the rutile crystal symmetry form of IrO₂ composition is knownand exhibits a semi-metallic character. Surprisingly, the triply chargedIr³⁺ valence state is possible using non-equilibrium growth methods andis a preferred state for application to incorporation with Ga₂O₃ and inparticular corundum crystal symmetry. Iridium has one of the highestmelting points and lowest vapor pressures when heated. The presentdisclosure utilizes electron-beam evaporation to form an elemental purebeam of Ir specie impinging upon a growth surface. If activated oxygenis supplied in coincidence and a corundum Ga₂O₃ surface presented forepitaxy, corundum crystal symmetry form of Ir₂O₃ composition can berealized. Furthermore, by co-depositing with pure elemental beams of Irand Ga with activated oxygen, compounds of (Ir_(x)Ga_(1−x))₂O₃ for0≤x≤1.0 can be formed. Furthermore, by co-depositing with pure elementalbeams of Ir and Al with activated oxygen, ternary compounds of(Ir_(x)Al_(1−x))₂O₃ for 0≤x≤1.0 can be formed. The addition of Ir to ahost metal oxide comprising at least one of Ga₂O₃, (Ga, Al)O₃ and Al₂O₃can reduce the effective bandgap. Furthermore, for Ir fractions ofx>0.25 the bandgap is exclusively indirect in nature.

Lithium (Li)

Lithium is a unique atomic specie especially when incorporated withoxygen. Pure Lithium metal readily oxidizes, and Lithium Oxide (Li₂O) isreadily formed using non-equilibrium growth methods of pure elemental Libeam and activated oxygen directed toward a growth surface of definitesurface crystal symmetry. Cubic crystal symmetry Li₂O exhibits a largeindirect bandgap Eg˜6.9 eV with lattice constants (a=b=c=4.54 A).Lithium is a mobile atom if present in a defective crystal structure,and it is this property which is exploited in Li-ion battery technology.The present disclosure, in contradistinction, seeks to rigidlyincorporate Li-atoms within a host crystal matrix comprising at leastone of Ga₂O₃, (Ga, Al)O₃ and Al₂O₃. Again, dilute Li concentrations canbe incorporated onto substitutional metal sites of Ga₂O₃, (Ga, Al)O₃ andAl₂O₃. For example, for a valence state of Li⁺¹ these compositions maybe utilized:

(Li₂O)_(x)(Ga₂O₃)_(1−x)═Li_(2x)Ga_(2(1−x))O_(3−2x), where 0≤x≤1; and

(Li₂O)_(x)(Al₂O₃)_(1−x)═Li_(2x)Al_(2(1−x))O_(3−2x), where 0≤x≤1.

Stoichiometric forms of Li_(2x)Ga_(2(1−x))O_(3−2x) for x=0.5 provide forLiGaO₂, and Li_(2x)Al_(2(1−x))O_(3−2x) for x=0.5 provide for LiAlO₂.

Both LiGaO₂ and LiAlO₂ crystalize in preferred orthorhombic and trigonalforms having direct and indirect bandgap energies, respectively, withE_(G)(LiGaO₂)=5.2 eV and E_(G)(LiALO₂)˜8 eV.

Of particular interest is the relatively small valence band curvature inboth suggesting a smaller hole effective mass compared to Ga₂O₃.

The lattice constants of LiGaO₂ (a=5.09 A, b=5.47, c=6.46 A) and LiAlO₂are (a=b=2.83 A, c=14.39 A). As bulk Li(Al, Ga)O₂ substrates may beutilized, orthorhombic and trigonal quaternary compositions such asLi(Al_(x)Ga_(1−x))O₂ may also be utilized thereby enabling UVLEDoperation for the optical emissive region.

Li impurity incorporation within even cubic NiO can enable improvedp-type conduction and can serve as a possible electrical injector regionfor holes applied to the UVLED.

Yet a further composition in some embodiments is ternary comprisingLithium-Nickel-Oxide Li_(x)Ni_(y)O_(z). Theoretical calculations provideinsight toward the possible higher valence states of Ni²⁺ and Li²⁺. Anelectronic composition comprising Li₂ ⁽⁺⁴⁾Ni⁺²O₃ ⁽⁻⁶⁾═Li₂NiO₃ may beutilized to create via non-equilibrium growth techniques forming amonoclinic crystal symmetry. It was found in accordance with the presentdisclosure that Li₂NiO₃ forms an indirect bandgap of E_(G)˜5 eV. Yetanother composition is the trigonal crystal symmetry (R3m) where Li⁺¹and Ni⁺¹ valence states form the composition Li₂NiO₂ having a directbandgap between s-like and p-like states of E_(G)=8 eV, however thestrong d-like states from Ni create crystal momentum independent midbandgap energy states continuous across all the Brillouin zones.

Nitrogen and Fluorine Anion Substitution

Furthermore, it has been found in accordance with the present disclosurethat selected anion crystal modifiers to the disclosed metal oxidecompositions may be selected from at least one of a nitrogen (N) andfluorine (F) specie. Similar to p-type activated hole concentrationcreation in binary Ga₂O₃ and ternary (GaxAl_(1−x))₂O₃ by substitutionalincorporation of a group-III metal cation site by a group-II metalspecie, it is further possible to substitute an oxygen anion site duringepitaxial growth by an activated Nitrogen atom (e.g., neutral atomicnitrogen species in some embodiments). In accordance with the presentdisclosure, dilute nitrogen incorporation within a Ga₂O₃ host wassurprisingly been found to stabilize monoclinic Ga₂O₃ compositionsduring epitaxy. Prolonged exposure of Ga₂O₃ during growth to acombination of elemental Ga and neutral atomic fluxes of simultaneousoxygen and nitrogen was found to form competing GaN-like precipitates.

It was also found in accordance with the present disclosure thatperiodically modulating the Ga₂O₃ growth by interrupting the Ga and Ofluxes periodically and preferentially exposing the terminated surfaceexclusively with activated atomic neutral nitrogen enables a portion ofthe surface to incorporate N on otherwise available O-sites within theGa₂O₃ growth. Spacing these N-layer growth interruptions by a distancegreater than 5 or more unit cells of Ga₂O₃ along the growth directionenables high density impurity incorporation aiding the achievement ofp-type conductivity character in Ga₂O₃.

This process may be utilized for both corundum and trigonal forms ofGa₂O₃.

In some embodiments, a combination approach of group-II metal cationsubstation and Nitrogen anion substation may be utilized for controllingthe p-type conductivity concentration in Ga₂O₃.

Fluorine impurity incorporation into Ga₂O₃ is also possible, howeverelemental fluorine sources are challenging. The present disclosureuniquely utilizes the sublimation of Lithium-Fluoride LiF bulk crystalwithin a Knudsen cell to provide a compositional constituent of both Liand F which is co-deposited during elemental Ga and Al beams under anactivated oxygen environment supplying the growth surface. Such atechnique enables the incorporation of Li and F atoms within anepitaxially formed Ga₂O₃ or LiGaO₂ host.

Examples of crystal symmetry structures formed using examplecompositions are now described and referred to in FIGS. 44A-44Z. Thecompositions shown are not intended to be limiting as discussed in theprevious section using the crystal modifiers.

An example of crystal symmetry groups 5000 that are possible for theternary composition of (Al_(x)Ga_(1−x))₂O₃ is shown in FIG. 44A. Thecalculated equilibrium crystal formation probability 5005 is a measureof the probability the structure will form for a given crystal symmetrytype. The space group nomenclature 5010 used in FIG. 44A is understoodby those skilled in the art.

The non-equilibrium growth methods described herein can potentiallyselect crystal symmetry types that are otherwise not accessible usingequilibrium growth methods (such as CZ). The general crystal classes ofcubic 5015, tetragonal, trigonal (rhombohedral/hexagonal) 5020,monoclinic 5025, and triclinic 5030 are shown in the inset of FIG. 44A.

For example, it was found in accordance with the present disclosure thatmonoclinic, trigonal and orthorhombic crystal symmetry types can be madeenergetically favorable by providing the kinematic growth conditionsfavoring exclusively a particular space group to be epitaxially formed.For example, as set out in TABLE I shown in FIG. 43A, the surface energyof a substrate can be selected by judicious preselection of the surfaceorientation presented for epitaxy.

FIG. 44B shows an example high-resolution x-ray Bragg diffraction(HRXRD) curves of a high quality, coherently strained, elasticallydeformed unit cell (i.e., the epilayer is termed pseudomorphic withrespect to the underlying substrate) strained ternary(Al_(x)Ga_(1−x))₂O₃ epilayer 5080 formed on a monoclinicGa₂O₃(010)-oriented surface 5045. The graph shows intensity 5035 as afunction of Ω−2 θ 5040. Two compositions (Al_(x)Ga_(1−x))₂O₃ x=0.15(5050) and x=0.25 (5065) are shown. The substrate is initially preparedby high temperature (>800° C.) desorption in an ultrahigh vacuum chamber(less than 5×10⁻¹⁰ Torr) of surface impurities.

The surface is monitored in real-time by reflection high energy electrondiffraction (RHEED) to assess atomic surface quality. Once a bright andstreaky RHEED pattern indicative of an atomically flat surface ofpredetermined surface reconstruction of the discontinuous surface atomdangling bond is apparent, the activated Oxygen source comprising anradiofrequency inductively coupled plasma (RF-ICP) is ignited to producea stream of substantially neutral atomic-Oxygen (O*) species and excitedmolecular neutral oxygen (O2*) directed toward the heated surface of thesubstrate.

The RHEED is monitored to show an oxygen-terminated surface. The sourceof elemental and pure Ga and Al atoms are provided by effusion cellscomprising inert ceramic crucibles radiatively heated by a filament andcontrolled by feedback sensing of a thermocouple advantageouslypositioned relative to the crucible to monitor the metal melttemperature within the crucible. High purity elemental metals are used,such as 6N to 7N or higher purity.

Each source beam flux is measured by a dedicated nude ion gauge that canbe spatially positioned in the vicinity of the center of the substrateto sample the beam flux at the substrate surface. The beam flux ismeasured for each elemental specie so the relative flux ratio can bepredetermined. During beam flux measurements a mechanical shutter ispositioned between the substrate and the beam flux measurement.Mechanical shutters also intersect the atomic beams emanating from eachcrucible containing each elemental specie selected to comprise epitaxialfilm.

During deposition the substrate is rotated so as to accumulate a uniformamount of atomic beam intersecting the substrate surface for a givenamount of deposition time. The substrate is heated radiatively frombehind by an electrically heated filament, in preference for oxidegrowth is the advantageous use of a Silicon-Carbide (SiC) heater. A SiCheater has the unique advantage over refractory metal filament heatersin that a broad near-to-mid infrared emissivity is possible.

Not well known to workers in the field of epitaxial film growth, is thatmost metal oxides have the attribute of relatively large opticalabsorption for near to far infrared wavelengths. The deposition chamberis preferentially actively and continuously pumped to achieve andmaintain vacuum in vicinity of 1 e-6 to 1 e-5 Torr during growth ofepitaxial films. Operating in this vacuum range, the evaporating metalsparticles from the surface of each effusion crucible acquire a velocitythat is essentially non-interacting and ballistic.

Advantageously positioning the effusion cell beam formed by the Clausingfactor of the crucible aperture and UHV large mean free path, thecollisionless ballistic transport of the effusion specie toward thesubstrate surface is ensured. The atomic beam flux from effusion typeheated sources is determined by the Arrhenius behavior of the particularelemental specie placed in the crucible. In some embodiments, Al and Gafluxes in the range of 1×10⁻⁶ Torr are measured at the substratesurface. The oxygen plasma is controlled by the RF power coupled to theplasma and the flow rate of the feedstock gas.

RF plasma discharges typically operate from 10 milliTorr to 1 Torr.These RF plasma pressures are not compatible with atomic layerdeposition process reported herein. To achieve activated oxygen beamfluxes in the range of 1×10⁻⁷ Torr to 1×10⁻⁵ Torr, a sealed fused quartzbulb with laser drilled apertures of the order of 100 microns indiameter are disposed across a circular end-face of the sealedcylindrical bulb. The said bulb is coupled to a helical wound coppertube and water-cooled RF antenna driven by an impedance matching networkand a high power 100 W-1 kW RF oscillator operating at, for example, 2MHz to 13.6 MHz or even 20 MHz.

The plasma is monitored using optical emission from the plasma dischargewhich provides accurate telemetry of actual species generated within thebulb. The size and number of the apertures on the bulb end face are theinterface of the plasma to the UHV chamber and can be predetermined toachieve compatible beam fluxes so as to maintain ballistic transportconditions for long mean free path in excess of the source to substratedistance. Other in-situ diagnostics enabling accurate control andrepeatability of film composition and uniformity include the use ofultraviolet polarized optical reflectometry and ellipsometry as well asa residual gas analyzer to monitor the desorption of species from thesubstrate surface.

Other forms of activated oxygen include the use of oxidizers such asOzone (O₃) and nitrous oxide (N₂O). While all forms work relativelywell, namely RF-plasma, O₃ and N₂O, RF plasma may be used in certainembodiments owing to the simplicity of point of use activation.RF-plasma, however, does potentially create very energetic charged ionspecies which can affect the material background conductivity type. Thisis mitigated by removing the apertures directly in the vicinity of thecenter of the plasma end plate coupled to the UHV chamber. The RFinduced oscillating magnetic field at the center of the solenoid of thecylindrical discharge tube will be maximal along the center axis.Therefore, removing the apertures providing line of sight from theplasma interior toward the growth surface removes the charged ionsspecie ballistically delivered to the epilayer.

Having briefly described the growth method, refer again to FIG. 44B. Themonoclinic Ga₂O₃(010)-oriented substrate 5045 is cleaned in-situ viahigh temperature in UHV conditions, such as at −800° C. for 30 mins. Thecleaned surface is then terminated with activated oxygen adatoms forminga surface reconstruction comprising oxygen atoms.

An optional homoepitaxial Ga₂O₃ buffer layer 5075 is deposited andmonitored for crystallographic surface improvement by in-situ RHEED. Ingeneral, Ga₂O₃ growth conditions using elemental Ga and activated oxygenrequires a flux ratio of ϕ(Ga):ϕ(O*)<1, that is atomic oxygen richconditions.

For flux ratios of Φ(Ga):Φ(O*)>1 an excess Ga atoms on the growthsurface is capable of attaching to surface bonded oxygen that canpotentially form a volatile Ga₂O_((g)) sub-oxide species—which thendesorbs from the surface and can remove material from the surface andeven etch the surface of Ga₂O₃. It was found in accordance with thepresent disclosure that for high Al content AlGaO₃ this etching processis reduced if not eliminated for Al %>50%. The etching process can beused to clean a virgin Ga₂O₃ substrate for example to aid in the removalof chemical mechanical polish (CMP) damage.

To initiate growth of AlGaO₃ the activated oxygen source is optionallyinitially exposed to the surface followed by opening both shutters foreach of the Ga and Al effusion cells. It was found experimentally inaccordance with the present disclosure that the sticking coefficient forAl is near unity whereas the sticking coefficient on the growth surfaceis kinetically dependent on the Arrhenius behavior of the desorbing Gaadatoms which depend on the growth temperature.

The relative x=Al % of the epitaxial (Al_(x)Ga_(1−x))₂O₃ film is relatedto x=Φ(Al)/[Φ(Ga)+Φ(Al)]. Clear high quality RHEED surfacereconstruction streaks are evident during deposition of(Al_(x)Ga_(1−x))₂O₃. The thickness can be monitored by in-situultraviolet laser reflectometry and the pseudomorphic strain statemonitored by RHEED. As the free-standing in-plane lattice constant ofmonoclinic crystal symmetry (Al_(x)Ga_(1−x))₂O₃ is smaller than theunderlying Ga₂O₃ lattice, the (Al_(x)Ga_(1−x))₂O₃ is grown under tensilestrain during elastic deformation.

The thickness 5085 of epilayer 5080 at which the elastic energy can bematched or reduced by inclusion of misfit dislocation within the growthplane is called the critical layer thickness (CLT), beyond this pointthe film can begin to grow as a partially or fully relaxed bulk-likefilm. The curves 5050 and 5065 are for the case of coherently strained(Al_(x)Ga_(1−x))₂O₃ films with thickness below the CLT. For the case ofx=0.15 the CLT is >400 nm and for x=0.25 CLT˜100 nm. The thicknessoscillations 5070 are also known as Pendellosung interference fringesand are indicative of highly coherent and atomically flat epitaxialfilm.

In experiments performed in relation to the present disclosure, growthof pure monoclinic Al₂O₃ epitaxial films directly on monoclinicGa₂O₃(010) surface achieved CLT<1 nm. It was further foundexperimentally that Al %>50% achieved low growth rate owing to theunique monoclinic bonding configuration of cations partitionedapproximately as 50% tetrahedral bonding sites and 50% octahedralbonding sites. It was found that Al adatoms prefer to incorporate atoctahedral bonding sites during crystal growth and have bonding affinityfor tetrahedral sites.

Superlattices (SLs) are created and directly applicable to UVLEDoperation utilizing the quantum size effect tuning mechanism forquantization of allowed energy levels within a narrower bandgap materialsandwiched between two potential energy barriers. Furthermore, SLs areexample vehicles for creating pseudo ternary alloys as discussed herein,further enabling strain management of the layers.

For example, monoclinic (Al_(x)Ga_(1−x))₂O₃ ternary alloy experiences anasymmetric in-plane biaxial tensile strain when epitaxial deposited uponmonoclinic Ga₂O₃. This tensile strain can be managed by ensuring thethickness of ternary is kept below the CLT within each layer comprisingthe SL. Furthermore, the strain can be balanced by tuning the thicknessof both Ga₂O₃ and ternary layer to manage the built-in strain energy ofthe bilayer pair.

Yet a further embodiment of the present disclosure is the creation of aternary alloy as bulk-like or SL grown sufficiently thick so as toexceed the CLT and form an essentially free-standing material that isstrain-free. This virtually strain-free relaxed ternary layer possessesan effective in-plane lattice constant a_(SL) which is parameterized bythe effective Al % composition. If then a first relaxed ternary layer isformed, followed by yet another second SL deposited directly upon therelaxed layer then the bilayer pair forming the second SL can be tunedsuch that the layers comprising the bilayer are in equal and oppositestrain states of tensile and compressive strain with respect to thefirst in-plane lattice constant.

FIG. 44C show an example SL 5115 formed directly on aGa₂O₃(010)-oriented substrate 5100.

The bilayer pairs comprising the SL 5115 are both monoclinic crystalsymmetry Ga₂O₃ and ternary (Al_(x)Ga_(1−x))₂O₃ (x=0.15) with SL periodΔ_(SL)=18 nm. The HRXRD 5090 shows the symmetric Bragg diffraction, andthe GIXR 5105 shows the grazing incidence reflectivity of the SL. Tenperiods are shown with extremely high crystal quality indicative of the(Al_(x)Ga_(1−x))₂O₃ having thickness<CLT.

The plurality of narrow SL diffraction peaks 5095 and 5110 is indicativeof coherently strained films registered with in-plane lattice constantmatching the monoclinic Ga₂O₃ (010)-oriented bulk substrate 5100. Themonoclinic crystal structure (refer to FIG. 37) having growth surfaceexposed of (010) exhibits a complex array of Ga and O atoms. In someembodiments, the starting substrate surface is prepared byO-terminations as described previously. The average Al % alloy contentof the SL represents a pseudo-bulk-like ternary alloy which can bethought of as an order atomic plane ternary alloy.

The SL comprising bilayers of [(Al_(xB)Ga_(1−xB))₂O₃/Ga₂O₃] has anequivalent Al % defined as:

${x_{Al}^{SL} = \frac{L_{B} \cdot x_{B}}{\Delta_{SL}}},$

where L_(B) is the thickness of the wider bandgap (Al_(xB)Ga_(1−xB))₂O₃layer. This can be directly determined by reference to the angularseparation and position of the zeroth-order diffraction peak SL^(n=0) ofthe SL with respect to the substrate peak 5102. Reciprocal lattice mapsshow that the in-plane lattice constant is pseudomorphic with theunderlying substrate and provides excellent application for the UVLED.

The tensile strain as shown in FIGS. 23A-23C can be used advantageouslytowards the formation of the optical emission region.

FIG. 44D shows yet further flexibility toward depositing ternarymonoclinic 5130 alloy (Al_(x)Ga_(1−x))₂O₃ directly upon yet anothercrystal orientation of monoclinic Ga₂O₃(001) substrate 5120.

Again, the best results are obtained by careful attention to highquality CMP surface preparation of the cleaved substrate surface. Thegrowth recipe in some embodiments utilizes in-situ activated oxygenpolish at high temperatures (e.g., 700-800° C.) using a radiativelyheated substrate via a high power and oxygen resistant radiativelycoupled heater. The SiC heater possesses the unique property of havinghigh near-to-far infrared emissivity. The SiC heater emissivity closelymatches the intrinsic Ga₂O₃ absorption features and thus couples well tothe radiative blackbody emission spectrum presented by the SiC heater.Region 5125 represents the O-termination process and the homoepitaxialgrowth of a high quality Ga₂O₃ buffer layer. The SL is then depositedshowing two separate growths with different ternary alloy compositions.

Shown in FIG. 44D are coherently strained epilayers of(Al_(x)Ga_(1−x))₂O₃ having thickness<CLT and achieving x˜15% (5135) andx˜30% (5140), relative to the (002) substrate peak 5122. Again, the highquality films are indicated by the presence of thickness interferencefringes.

Discovering further that SL structures are also possible on the (001)oriented monoclinic Ga₂O₃ substrate 5155, the results are shown in FIG.44E.

Clearly, HRXRD 5145 and GIXR 5158 demonstrate a high quality coherentlydeposited SL. Peak 5156 is the substrate peak. The SL diffraction peaks5150 and 5160 enable direct measurement of the SL period, and theSL^(n=0) peak enables the effective Al % of SL to be determined. Forthis case a ten period SL[(Al_(0.18)Ga_(0.92))₂O₃/Ga₂O₃] having periodΔ_(SL)=8.6 nm is shown.

Demonstrating an example application of the versatility of the metaloxide film deposition method disclosed herein, refer to FIG. 44F. Twodissimilar crystal symmetry type structures are epitaxially formed alonga growth direction as defined by FIG. 18. A substrate 5170 (peak 5172)comprising monoclinic Ga₂O₃(001)-oriented surface is presented forhomoepitaxy of a monoclinic Ga₂O₃ 5175. Next a cubic crystal symmetryNiO epilayer 5180 is deposited. The HRXRD 5165 and GIXR 5190 show thetopmost NiO film peak 5185 of thickness 50 nm has excellent atomicflatness and thickness fringes 5195.

In one example, mixing-and-matching crystal symmetry types can befavorable to a given material composition that is advantageous for agiven function comprising the UVLED (refer FIG. 1) thereby increasingthe flexibility for optimizing the UVLED design. Ni_(x)O (0.5<x≤1representing metal vacancy structures are possible), Li_(x)Ni_(y)O_(n),Mg_(x)Ni_(1−x)O and Li_(x)Mg_(y)Ni_(z)O_(n) are compositions that may beutilized favorably for integration with AlGaO₃ materials comprising theUVLED.

As NiO and MgO share very close cubic crystal symmetry and latticeconstants, they are advantageous for bandgap tuning application fromabout 3.8 to 7.8 eV. The d-states of Ni influence the optical andconductivity type of the MgNiO alloy and can be tailored for applicationto UVLED type devices. A similar behavior is found for the selectiveincorporation of Ir into corundum crystal symmetry ternary alloy(Ir_(x)Ga_(1−x))₂O₃ which exhibits advantageous energy position withinthe E-k dispersion due to the Iridium d-state orbitals for creation ofp-type conductivity.

Yet a further example of the metal oxide structures is shown in FIG.44G. A cubic crystal symmetry MgO (100)-oriented surface of a substrate5205 (corresponding to peak 5206) is presented for direct epitaxy ofGa₂O₃. It was found in accordance with the present disclosure that thesurface of MgO can be selectively modified to create a cubic crystalsymmetry form of Ga₂O₃ epilayer 5210 (peaks 5212 for gamma Ga₂O₃) thatacts as an intermediate transition layer for subsequent epitaxy ofmonoclinic Ga₂O₃(100) 5215 (peaks 5214 and 5217). Such a structure isrepresented by the growth process shown in FIG. 20A.

First a prepared clean MgO (100) surface is presented for MgOhomoepitaxy. The magnesium source is a valved effusion source comprising7N purity Mg with a beam flux of ˜1×10⁻¹⁰ Torr in the presence ofactive-oxygen supplied with ϕ(Mg):ϕ(O*)<1 and substrate surface growthtemperature from 500-650° C.

The RHEED is monitored to show improved and high quality surfacereconstruction of MgO surface of the epitaxial film. After about 10-50nm of MgO homoepitaxy the Mg source is closed and the substrate elevatedto a growth temperature of about 700° C. while under a protective fluxof O*. Then the Ga source is exposed to the growth surface and the RHEEDis observed to instantaneous change surface reconstruction toward acubic crystal symmetry Ga₂O₃ epilayer 5210. After about 10-30 nm ofcubic Ga₂O₃ (known also as the gamma-phase) it is observed via directobservation of RHEED the characteristic monoclinic surfacereconstruction of Ga₂O₃(100) appears and remains as the most stablecrystal structure. A Ga₂O₃(100)-oriented film of 100 nm is deposited,with HRXRD 5200 and GIXR 5220 showing peak 5214 for beta-Ga₂O₃(200) andpeak 5217 for beta-Ga₂O₃(400). Such fortuitous crystal symmetryalignments are rare but highly advantageous for the application towardUVLED.

Yet another example of a complex ternary metal oxide structure appliedfor UVLED is disclosed in FIG. 44H. The HRXRD 5225 and GIXR 5245 showexperimental realization of a superlattice comprising alanthanide-aluminum-oxide ternary integrated with corundum Al₂O₃epilayers.

The SL comprises corundum crystal symmetry (Al_(x)Er_(1−x))₂O₃ ternarycomposition with the lanthanide selected from Erbium grownpseudomorphically with corundum Al₂O₃. Erbium is presented to thenon-equilibrium growth via a sublimating 5N purity Erbium source usingan effusion cell. The flux ratio of ϕ(Er):ϕ(Al)˜0.15 was used with theoxygen-rich condition of [ϕ(Er)+ϕ(Al)]:ϕ(O*)]<1 at a growth temperatureof about 500° C.

Of particular note is the ability for Er to crack molecular oxygen atthe epilayer surface and therefore the total oxygen overpressure islarger than the atomic oxygen flux. An A-plane Sapphire (11-20)substrate 5235 is prepared and heated to about 800° C., and exposed toan activated Oxygen polish. It was found in this example that theactivated oxygen polish of the bare substrate surface dramaticallyimproves the subsequent epilayer quality. Next a homoepitaxial corundumAl₂O₃ layer is formed and monitored by RHEED showing excellent crystalquality and atomically flat layer-by-layer deposition. Then a ten periodSL is deposited and shown as the satellite peaks 5230 and 5240 in theHRXRD 5225 and GIXR 5245 scans. Clearly evident are the Pendellosungfringes indicating excellent coherent growth.

The effective alloy composition of the (Er_(xSL)Al_(1−xSL))₂O₃ of the SLcan be deduced by position of the zeroth order SL peak SL^(n=0) relativeto the (110) substrate peak 5235. It is found xSl˜0.15 is possible andthat the (Al_(x)Er_(1−x))₂O₃ layer forming the SL period has corundumcrystal symmetry. This discovery is particularly important forapplication to UVLED wherein FIG. 44I discloses the E-K band structure5250 of corundum (Al_(x)Er_(1−x))₂O₃ is indeed a direct bandgap materialhaving E_(G)>6 eV. The electron energy 1066 is plotted as a function ofthe crystal wave vectors 1067. The conduction band minimum 5265 andvalence band 5260 is maximum at the Brillouin-zone center 5255 (k=0).

Next in FIG. 44J is demonstrated yet a further ternarymagnesium-gallium-oxide cubic crystal symmetry Mg_(x)Ga_(2(1−x))O_(3−2x)material composition integrable with Ga₂O₃. Shown is the HRXRD 5270 andGIXR 5290 experimental realization of a superlattice comprising a 10period SL[Mg_(x)Ga_(2(1−x))O³⁻²/Ga₂O₃] deposited upon a monoclinicGa₂O₃(010) oriented substrate 5275 (corresponding to peak 5277). The SLternary alloy composition is selected from x=0.5 with thickness of 8 nmand Ga₂O₃ of 8 nm. The SL period is Δ_(SL)=16 nm with average Mg % ofx_(Mg) ^(SL)=x.L_(MgGaO)/Δ_(SL). The diffraction satellite peaks 5280and 5295 report slight diffusion of Mg across the SL interfaces whichcan be alleviated by growing at a lower temperature. The band structureof Mg_(x)Ga_(2(1−x))O_(3−2x) x=0.5 is particularly useful forapplication toward UVLED. FIG. 44K reports the calculated energy bandstructure 5300 is direct in character (refer to band extrema 5315 and5310 and k=0 5305) with bandgap of E_(G)˜5.5 eV.

The ability for the monoclinic Ga₂O₃ crystal symmetry to integrate withcubic MgAl₂O₄ crystal symmetry substrates is presented in FIG. 44L. Ahigh quality single crystal substrate 5320 (peak 5322) comprisingMgAl₂O₄ spinel is cleaved and polished to expose the (100)-orientedcrystal surface. The substrate is prepared and polished using activeoxygen at elevated temperature (˜700° C.) under UHV conditions (<1 e-9Torr). Keeping the substrate at growth temperature of 700° C. theMgGa₂O₄ film 5330 is initiated showing excellent registration to thesubstrate. After about 10-20 nm the Mg is shuttered and only Ga₂O₃ isdeposited as the topmost film 5325. The GIXR film flatness is excellentshowing thickness fringes 5340 indicating a >150 nm film. The HRXRDshows transition material MgGa₂O₄ corresponding to peaks 5332 andGa₂O₃(100)-oriented epilayer of peaks 5327 indicative of monocliniccrystal symmetry. In some embodiments, hexagonal Ga₂O₃ can also bedeposited epitaxially.

The monoclinic Ga₂O₃ (−201)-oriented crystal plane features uniqueattributes of a hexagonal oxygen surface matrix with in-plane latticespacing acceptable for registering wurtzite-type hexagonal crystalsymmetry materials. For example, as shown in diagram 5345 of FIG. 44Mwurtzite ZnO 5360 (peak 5367) is deposited on an oxygen terminatedGa₂O₃(−201)-oriented surface of a substrate Zn_(x)Ga_(2(1−x))O_(3−2x)5350 (peak 5352). The Zn is supplied by sublimation of 7N purity Zncontained within an effusion cell. The growth temperature is selectedfrom 450-650° C. for ZnO and exhibits extremely bright and sharp narrowRHEED streaks indicative high crystal quality. Peak 5362 represents(Al_(x)Ga_(1−x))₂O₃. Peak 5355 represents a transition layer.

Next a ternary zinc-gallium-oxide epilayer Zn_(x)Ga_(2(1−x))O_(3−2x)5365 is deposited by co-deposition of Ga and Zn and active oxygen at500° C. The flux ratio of [ϕ(Zn)+ϕ(Ga)]:ϕ(O*)<1 and the metal beam fluxratio ϕ(Zn):ϕ(Ga) is chosen to achieve x˜0.5. Zn desorbs at much lowersurface temperatures than Ga and is controlled in part by absorptionlimited process depending on surface temperature dictated by theArrhenius behavior of Zn adatoms.

Zn is a group metal and substitutes advantageously on available Ga-sitesof the host crystal. In some embodiments, Zn can be used to alter theconductivity type of the host for dilute x≤0.1 concentrations ofincorporated Zn. The peak 5355 labelled Zn_(x)Ga_(2(1−x))O_(3−2x) showsthe transition layer formed on the substrate showing low Ga % formationof Zn_(x)Ga_(2(1−x))O_(3−2x). This suggests strongly a high miscibilityof Ga and Zn in the ternary offering non-equilibrium growth of fullrange of alloys 0≤x≤1. For the case of x=0.5 inZn_(x)Ga_(2(1−x))O_(3−2x) offers the cubic crystal symmetry form an E-kband structure as shown in diagram 5370 of FIG. 44N.

The indirect bandgap shown by band extrema 5375 and 5380 can be shapedusing SL band engineering as shown in FIG. 27. The valence banddispersion 5385 showing maxima at k≠0 can be used to create a SL periodthat can advantageously map the maxima back to an equivalent energy atzone center thereby creating a pseudo-direct bandgap structure. Such amethod is claimed in its entirety for application to the formation ofoptoelectronic devices such as UVLEDs as referred to in the presentdisclosure.

As explained in the present disclosure, there is a large design spaceavailable for crystal modifiers to the Ga₂O₃ and Al₂O₃ host crystalsthat can be exploited for application to UVLEDs.

Yet a further example is now disclosed where the growth conditions canbe tuned to preselect a unique crystal symmetry type of Ga₂O₃, namelymonoclinic (beta-phase) or hexagonal (epsilon or kappa phase).

FIG. 44O shows a specific application of the more general methoddisclosed in FIG. 19.

A prepared and clean surface of corundum crystal symmetry type ofsapphire C-plane substrate 5400 is presented for epitaxy.

The substrate surface is polished via active oxygen at elevatedtemperature >750° C. and such as −800-850° C. This creates an oxygenterminated surface 5405. While maintaining the high growth temperature,a Ga and active oxygen flux is directed toward the epi-surface and thesurface reconstruction of bare Al₂O₃ is modified to either a corundumGa₂O₃ thin template layer 5396 or a low Al % corundum(Al_(x)Ga_(1−x))₂O₃x<0.5 is formed by an additional co-deposited Alflux. After about 10 nm of the template layer 5396 the Al flux is closedand Ga₂O₃ is deposited. Maintaining a high growth temperature and a lowAl % template 0≤x<0.1 favors exclusive film formation of monocliniccrystal structure epilayer 5397.

If after the initial template layer 5396 formation the growthtemperature is reduced to about 650-750° C. then the Ga₂O₃ favorsexclusively the growth of a new type of crystal symmetry structurehaving hexagonal symmetry. The hexagonal phase of Ga₂O₃ is also favoredby x>0.1 template layer. The unique properties of the hexagonal crystalsymmetry Ga₂O₃ 5420 composition is discussed later. The experimentalevidence for the disclosed process of growing the epitaxial structure5395 is provided in FIG. 44P, showing the HRXRD 5421 for two distinctgrowth process outcomes of phase pure monoclinic Ga₂O₃ and hexagonalcrystal symmetry Ga₂O₃. The HRXRD scan shows the C-planeAl₂O₃(0001)-oriented substrate Bragg diffraction peaks of corundumAl₂O₃(0006) 5465 and Al₂O₃(0012) 5470. For the case of monoclinic Ga₂O₃topmost epitaxial film, the diffraction peaks indicated by 5445, 5450,5455, and 5460 represent sharp single crystal monoclinic Ga₂O₃(−201),Ga₂O₃(−204), Ga₂O₃(−306) and Ga₂O₃(−408).

The orthorhombic crystal symmetry can further exhibit an advantageousproperty of possessing a non-inversion symmetry. This is particularlyadvantageous for allowing electric dipole transition between theconduction and valence band edges of the band structure at zone-center.For example, wurtzite ZnO and GaN both exhibit crystal symmetry havingnon-inversion symmetry. Likewise, orthorhombic (namely the space group33 Pna21 crystal symmetry) has a non-inversion symmetry which enableselectric dipole optical transitions.

Conversely, for the growth process of hexagonal Ga₂O₃, the peaks 5425,5430, 5435 and 5440 represent sharp single crystal hexagonal crystalsymmetry Ga₂O₃(002), Ga₂O₃(004), Ga₂O₃(006), and Ga₂O₃(008).

The importance of achieving hexagonal crystal symmetry Ga₂O₃ and alsohexagonal (Al_(x)Ga_(1−x))₂O₃ is shown in FIG. 44Q.

The energy band structure 5475 shows the conduction band 5480 andvalence band 5490 extrema are both located at the Brillouin-zone center5485 and is therefore advantageous for application to UVLED.

Single crystal sapphire is one of the most mature crystalline oxidesubstrates. Yet another form of Sapphire is the corundum M-plane surfacewhich can be used advantageously to form Ga₂O₃ and AlGaO₃ and othermetal oxides discussed herein.

For example, it has been found experimentally in accordance with thepresent disclosure that the surface energy of Sapphire exhibited byspecific crystal planes presented for epitaxy can be used to preselectthe type of crystal symmetry of Ga₂O₃ that is epitaxially formedthereon.

Consider now FIG. 44R disclosing the utility of an M-plane corundumAl₂O₃ substrate 5500. The M-plane is the (1-100) oriented surface andcan be prepared as discussed previously and atomically polished in-situat elevated growth temperature of 800° C. while exposed to an activatedoxygen flux. The oxygen terminated surface is then cooled to 500-700°C., such as 500° C. in one embodiment, and a Ga₂O₃ film is epitaxiallydeposited. It was found that in excess of 100-150 nm of corundum crystalsymmetry Ga₂O₃ can be deposited on M-plane sapphire and about 400-500 nmof corundum (Al_(x)Ga_(1−x))₂O₃ for x˜0.3-0.45. Of particular interest,corundum (Al₀₃Ga_(0.7))₂O₃ exhibits a direct bandgap and is equivalentto the energy gap of wurtzite AlN.

The HRXRD 5495 and GIXR 5540 curves show two separate growths on M-planesapphire 5500. High quality single crystal corundum Ga₂O₃ 5510 and(Al₀₃Ga_(0.7))₂O₃ 5505 are clearly shown with respect to the corundumAl₂O₃ substrate peak 5502. Therefore, M-plane oriented AlGaO₃ films arepossible on M-plane Sapphire. The GIXR thickness oscillation 5535 isindicative of atomically flat interfaces 5520 and films 5530. Curve 5155shows that there are no other crystal phases of Ga₂O₃ other than thecorundum phase (rhombohedral crystal symmetry).

For completeness, it has also been found in accordance with the presentdisclosure that various metal oxides can also be used to exploit eventhe most technologically mature semiconductor substrate, namely Silicon.For example, while bulk Ga₂O₃ substrates are desirable for theircrystallographic and electronic properties, they are still moreexpensive to produce than single crystal substrates and furthermorecannot scale as easily as Si to large wafer diameter substrates, forexample up to 450 mm diameter for Si.

Therefore, embodiments include developing functional electronic Ga₂O₃films directly on Silicon. To this end a process has been developedspecifically for this application.

Referring now to FIG. 44S, there are shown the results of oneexperimentally developed process for depositing monoclinic Ga₂O₃ filmson large area Silicon substrates.

A single crystal high quality monoclinic Ga₂O₃ epilayer 5565 is formedon a cubic transition layer 5570 comprising ternary (Ga_(1−x)Er_(x))₂O₃.The transition layer is deposited using a compositional grading whichcan be abrupt or continuous. The transition layer can also be a digitallayer comprising a SL of layers of[(Ga_(1-31 x)Er_(x))₂O₃/(Ga_(1−y)Er_(y))₂O₃] wherein x and y areselected from 0≤x, y≤1. The transition layer is deposited optionally ona binary bixbyite crystal symmetry Er₂O₃(111)-oriented template layer5560 deposited on a Si(111)-oriented substrate 5555. Initially theSi(111) is heated in UHV to 900° C. or more but less than 1300° C. todesorb the native SiO₂ oxide and remove impurities.

A clear temperature dependent surface reconstruction change is observedand can be used to in-situ calibrate the surface growth temperaturewhich occurs at 830° C., and is only observable for a pristine Sisurface devoid of surface SiO₂. Then the temperature of the Si substrateis reduced to 500-700° C. to deposit the (Ga_(1−y)Er_(y))₂O₃ film(s) andthen increased slightly to favor epitaxial growth of monoclinicGa₂O₃(−201)-oriented active layer film. If Er₂O₃ binary is used, thenactivated oxygen is not necessary and pure molecular oxygen can be usedto co-deposit with pure Er beam flux. As soon as Ga is introduced theactivated oxygen flux is necessary. Other transition layers are alsopossible and can be selected from a number of ternary oxides describedherein. The HRXRD 5550 shows the cubic (Ga_(1−y)Er_(y))₂O₃ peak 5572along with the bixbyite Er₂O₃(111) and (222) peaks 5562. The monoclinicGa₂O₃ (−201), (−201), (−402) peaks are also observed as peaks 5567, andthe Si(111) substrate as peaks 5557.

One application of the present disclosure is the use of cubic crystalsymmetry metal oxides for the use of transition layers betweenSi(001)-oriented substrate surfaces to form Ga₂O₃(001) and(Al_(x)Ga)₂O₃(001)-oriented active layer films. This is particularlyadvantageous for high volume manufacture.

Interest herein is directed toward exploiting transparent substratesthat can accommodate a wide variety of metal oxide compositions andcrystal symmetry types. In particular, again it is reiterated that theAl₂O₃, (Al_(x)Ga_(1−x))₂O₃ and Ga₂O₃ materials are of great interest andthe opportunity for accessing the entire miscibility range of Al % x in(Al_(x)Ga_(1−x))₂O₃ and Ga % y in (Al_(1−y)Ga_(y))₂O₃ can be addressedby corundum crystal symmetry type compositions.

Reference shall now be made to the examples in FIGS. 44T-44X.

FIG. 44T discloses high quality single crystal epitaxy of corundumGa₂O₃(110)-oriented film on Al₂O₃(11-20)-oriented substrate (i.e.,A-plane Sapphire). The surface energy of the A-plane Al₂O₃ surface canbe used to grow exceptionally high quality corundum Ga₂O₃ and ternaryfilms of corundum (Al_(x)Ga_(1−x))₂O₃ where 0≤x≤1 for the entire alloyrange. Ga₂O₃ can be growth up to a CLT of about 45-80 nm and the CLTincreases dramatically with the introduction of Al to form the ternary(Al_(x)Ga_(1−x))₂O₃.

Homoepitaxial growth of corundum Al₂O₃ is possible at a surprisinglywide growth window range. Corundum AlGaO₃ can be grown from roomtemperature up to about 750° C. All growths, however, require anactivated oxygen (viz., atomic oxygen) flux to be well in excess of thetotal metal flux, that is, oxygen rich growth conditions. Corundumcrystal symmetry Ga₂O₃ films are shown in the HRXRD 5575 and GIXR 5605scan of two separate growths for different thickness films on A-planeAl₂O₃ substrates. The substrate 5590 surface (corresponding to peak5592) is oriented in the (11-20) plane and O-polished at elevatedtemperature at about 800° C.

The activated oxygen polish is maintained while the growth temperatureis reduced to an optimal range of 450-600° C., such as 500° C. Then anAl₂O₃ buffer 5595 is optionally deposited for 10-100 nm and then theternary (Al_(x)Ga_(1−x))₂O₃ epilayer 5600 is formed by co-depositingwith suitably arranged Al and Ga fluxes to achieve the desired Al %.Oxygen-rich conditions are mandatory. Curves 5580 and 5585 show examplex=O Ga₂O₃ films 5600 of 20 and 65 nm respectively.

The Pendellosung interference fringes in both the HRXRD and GIXRdemonstrate excellent coherent growth, and transmission electronmicroscopy (TEM) confirm off-axis XRD measurements that defect densitiesbelow 10⁷ cm⁻³ are possible.

Corundum Ga₂O₃ films on A-plane Al₂O₃ in excess of about 65 nm showrelaxation as evidenced in reciprocal lattice mapping (RSM) but howevermaintain excellent crystal quality for film>CLT.

Yet other methods for further improvement in the CLT of binary Ga₂O₃films on A-plane Al₂O₃ are also possible. For example, during the hightemperature O-polish step of a virgin Al₂O₃ substrate surface, thesubstrate temperature can be maintained at about 750-800° C. At thisgrowth temperature the Ga flux can be presented along with the activatedoxygen and a high temperature phenomenon can occur. It was found inaccordance with the present disclosure that Ga effectively diffuses intothe topmost surface of the Al₂O₃ substrate forming an extremely highquality corundum (Al_(x)Ga_(1−x))₂O₃ template layer with 0<x<1. Thegrowth can either be interrupted or continued while the substratetemperature is reduced to about 500° C. The template layer then acts asan in-plane lattice matching layer that is closer to Ga₂O₃ and thus athicker CLT is found for the epitaxial film.

Having established the unique properties of A-plane surfaces and withreference to the surface energy trend disclosed in FIG. 20B, bandgapmodulated superlattice structures are also shown to be possible.

FIG. 44U shows unique attributes of binary Ga₂O₃ and binary Al₂O₃epilayers used to form a SL structure on an A-plane Al₂O₃ substrate 5625(corresponding to peak 5627). The excellent SL HRXRD 5610 and GIXR 5630data show a plurality of high quality SL Bragg diffraction satellitepeaks 5615 and 5620 having period Δ_(SL)=9.5 nm. Not only are the fullwidth at half maximum (FWHM) of each satellite peak 5615 very small,there are also clearly observed the inter-peak oscillations of thePendellosung fringes. For N=10 periods of SL, there exist N−2Pendellosung oscillations as shown in both the HRDRD and GIXR. Thezeroth order SL peak SL^(n=0) is indicative of the average alloy Al % ofthe digital alloy formed by the SL and is x_(Al) ^(SL)=0.85. This levelof crystalline perfection is rarely observed in many other non-oxidecommercially relevant material systems and is noted to be comparable toextremely mature GaAs/AlAs group-III-Arsenide material systems depositedon GaAs substrates. Such low defect density SL structures are necessaryfor high performance UVLED operation.

Image 5660 in FIG. 44V demonstrates the crystal quality observed for anexample [Al₂O₃/Ga₂O₃] SL 5645 deposited on A-plane sapphire 5625.Clearly evident is the contrast in Ga and Al specie showing the abruptinterfaces between the nanometer scale films 5650 and 5655 comprisingthe SL period.

Closer inspection of image 5660 shows the region labelled 5635 which isdue to the high temperature Ga intermixing process described above. TheAl₂O₃ buffer layer 5640 imparts a small strain to the SL stack. Carefulattention is paid to maintaining the Ga₂O₃ film thickness to well belowthe CLT to create high quality SL. However, strain accumulation canresult and other structures such as growing the SL structure on arelaxed buffer composition midway between the composition endpoints ofthe materials comprising the SL is possible in some embodiments.

This enables strain symmetrization to be engineered wherein the layerpairs forming the period of the superlattice can have equal and oppositein-plane strain. Each layer is deposited below the CLT and experiencesbiaxial elastic strain (thereby inhibiting dislocation formation at theinterfaces). Therefore some embodiments include engineering a SLdisposed on a relaxed buffer layer that enables the SL to accumulatezero strain and thus can be grown effectively strain-free withtheoretically infinite thickness.

Yet a further application of corundum film growth can be demonstrated onyet another advantageous Al₂O₃ crystal surface, namely the R-plane(1-102).

FIG. 44W shows the ability to epitaxially deposit thick ternary corundum(Al_(x)Ga_(1-x))₂O₃ films on R-plane corundum Al₂O₃. The HRXRD 5665shows an R-plane Al₂O₃ substrate 5675 that is prepared using a hightemperature O-polish and co-deposition of Al and Ga while reducing thegrowth temperature from 750 to 500° C. forming region 5680. Region 5680is an optional surface layer modification to the sapphire substratesurface, such as an oxygen-terminated surface. The excellent highquality ternary epilayer 5670 (corresponding to XRD peak 5672)demonstrates sharp Pendellosung fringes 5680 and provides an alloycomposition of x=0.64 with respect to the substrate peak 5677. The filmthickness for this case is about 115 nm. Also shown in FIG. 44W is theangular separation of symmetric Bragg peaks 5685 of the pseudomorphiccorundum Ga₂O₃ epilayer.

Again, high utility is placed on creating bandgap epilayer films thatmay be configured or engineered to construct the required functionalregions for the UVLED. In this manner, strain and composition are toolsthat may be employed for manipulating known functional properties of thematerials for application to UVLEDs in accordance with the presentdisclosure.

FIG. 44X shows an example of a high quality superlattice structurepossible for R-plane Al₂O₃(1-102) oriented substrates.

The HRXRD 5690 and GIXR 5710 are shown for an example SL epitaxiallyformed on R-plane Al₂O₃(1-102) substrate 5705 (corresponding to peak5707).

The SL comprises a 10 period [ternary/binary] bilayer pair of[(Al_(x)Ga_(1−x))₂O₃/Al₂O₃] where x=0.50. The SL period Δ_(SL)=20 nm.The plurality of SL Bragg diffraction peaks 5695 and reflectivity peaks5715 indicate coherently grown pseudomorphic structure. The zeroth orderSL diffraction peak SL^(n=0) 5700 indicates an effective digital alloyx_(SL) of the SL as comprising (Al_(xSL)Ga_(1−xSL))₂O₃ where x_(SL)=0.2.

Such highly coherent and largely dissimilar bandgap materials used tocreate epitaxial SL with abrupt discontinuities at the interfaces may beemployed for the formation of quantum confined structures as disclosedherein for application to optoelectronic devices such as UVLEDs.

The conduction and valence band energy discontinuity available at theAl₂O₃/Ga₂O₃ heterointerface for corundum crystal symmetry (R3c) is:

ΔE_(R3c) ^(C)=E_(Al) ₂ _(O) ₃ ^(C)−E_(Ga) ₂ _(O) ₃ ^(C)=3.20 eV

ΔE_(R3c) ^(V)=E_(Al) ₂ _(O) ₃ ^(V)−E_(Ga) ₂ _(O) ₃ ^(V)=0.12 eV

Also, for the monoclinic crystal symmetry (C2m) heterointerface the bandoffsets are:

ΔE_(C2m) ^(C)=E_(Al) ₂ _(O) ₃ ^(C)−E_(Ga) ₂ _(O) ₃ ^(C)=2.68 eV

ΔE_(C2m) ^(V)=E_(Al) ₂ _(O) ₃ ^(V)−E_(Ga) ₂ _(O) ₃ ^(V)=0.34 eV

Some embodiments also include creating a potential energy discontinuityby creation of Ga₂O₃ layers having an abrupt change in crystal symmetry.

For example, it is disclosed herein that corundum crystal symmetry Ga₂O₃can be directly epitaxially deposited on monoclinic Ga₂O₃(110)-orientedsurfaces. Such a heterointerface produces band offsets given by:

ΔE_(Ga) ₂ _(O) ₃ ^(C)=E_(R3c) ^(C)−E_(C2m) ^(C)˜0.50 eV

ΔE_(Ga) ₂ _(O) ₃ ^(V)=E_(R3c) ^(V)−E_(C2m) ^(V)˜0.10 eV

These band offsets are sufficient to create quantum confined structuresas will be described below.

As yet another example of embodiments of complex metal oxideheterostructures, refer to FIG. 44Y wherein a cubic MgO epilayer 5730 isformed directly on a spinel MgAl₂O₄(100) oriented substrate 5725. TheHRXRD 5720 shows the cubic MgAl₂O₄(h 0 0), h=4, 8 substrate Braggdiffraction peaks 5727 and the epitaxial cubic MgO peaks 5737corresponding to the MgO epilayer 5730. The lattice constant of MgO isalmost exactly twice the lattice constant of MgAl₂O₄ and thus createsunique epitaxial coincidence for in-plane lattice registration at theheterointerface.

Clearly a high quality MgO(100)-oriented epilayer is formed as evidencedby the narrow FWHM. Next a monoclinic layer of Ga₂O₃ 5735 is formed onthe MgO layer 5730. The Ga₂O₃(100) oriented film is evidenced by the5736 Bragg diffraction peak.

The interest in cubic MgAl₂O₄ and Mg_(x)Al_(2(1−x))O_(3−2x) ternarystructures is due to the direct and large bandgap possible.

Graph 5740 of FIG. 44Z shows the energy band structure forMg_(x)Al_(2(1−x))O_(3−2x) x˜0.5 showing a direct bandgap 5745 formedbetween the conduction band 5750 and valence band 5755 extrema.

Some embodiments also include growing directly Ga₂O₃ onLanthanum-Aluminum-Oxide LaAlO₃(001) substrates.

The example structures disclosed in FIGS. 44A-44Z are for the purpose ofdemonstrating some of the possible configurations applicable for use inat least a portion of a UVLED structure. The wide variety of compatiblemixed symmetry type heterostructures is a further attribute of thepresent disclosure. As would be appreciated, other configurations andstructures are also possible and consistent with the present disclosure.

The aforementioned unique properties of the AlGaO₃ material system canbe applied to formation of a UVLED. FIG. 45 shows an example lightemitting device structure 1200 in accordance with the presentdisclosure. Light emitting device 1200 is designed to operate such thatoptically generated light can be out-coupled vertically through thedevice. Device 1200 comprises a substrate 1205, a first conductivityn-type doped AlGaO₃ region 1210, followed by a not-intentionally doped(NID) intrinsic AlGaO₃ spacer region 1215, followed by a multiplequantum well (MQW) or superlattice 1240 formed using periodicrepetitions of (Al_(x)Ga_(1−x))₂O₃/(Al_(y)Ga_(1−y))₂O₃ wherein thebarrier layer comprises the larger bandgap composition 1220 and the welllayer comprises the narrower bandgap composition 1225.

The total thickness of the MQW or SL 1240 is selected to achieve thedesired emission intensity. The layer thicknesses comprising the unitcell of the MQW or SL 1240 are configured to produce a predeterminedoperating wavelength based on the quantum confinement effect. Next anoptional AlGaO₃ spacer layer 1230 separates the MQW/SL from the p-typeAlGaO₃ layer 1235.

Spatial energy band profiles using the k=0 representation are disclosedin FIGS. 46, 47, 49, 51 and 53 which are graphs of spatial band energy1252 as a function of growth direction 1251. The n-type and p-typeconductivity regions 1210 and 1235 are selected from monoclinic orcorundum compositions of (Al_(x)Ga_(1−x))₂O₃, where x=0.3, followed by aNID 1215 of the same composition x=0.3. The MQW or SL 1240 is tuned bykeeping the thickness of both the well and barrier layers the same ineach design 1250 (FIGS. 46, 47), 1350 (FIG. 49), 1390 (FIG. 51) and 1450(FIG. 53).

The composition of the well is varied from x=0.0, 0.05, 0.10 and 0.20,and the barrier is fixed to y=0.4 for the bi-layer pairs(Al_(x)Ga_(1−x))₂O₃/(Al_(y)Ga_(1−y))₂O₃. These MQW regions are locatedat 1275, 1360, 1400 and 1460. The thickness of the well layer isselected from at least 0.5xa_(w) to 10xa_(w) the unit cell (aw latticeconstant) of the host composition. For the present case, one unit cellis chosen. The periodic unit cell thickness can be relatively large asthe corundum and monoclinic unit cells are relatively large. However,sub-unit-cell assemblies may be utilized in some embodiments. MQW region1275 in FIG. 47 is configured for intrinsic or non-intentionally dopedlayer combination comprising Ga₂O₃/(Al_(0.4)Ga_(0.6))₂O₃. MQW region1360 in FIG. 49 is configured for intrinsic or non-intentionally dopedlayer combination comprising(Al_(0.05)Ga_(0.95))₂O₃/(Al_(0.4)Ga_(0.6))₂O₃. MQW region 1400 in FIG.51 is configured for intrinsic or non-intentionally doped layercombination comprising (Al_(0.1)Ga_(0.9))₂O₃/(Al_(0.4)Ga_(0.6))₂O₃. MQWregion 1460 in FIG. 53 is configured for intrinsic or non-intentionallydoped layer combination comprising(Al_(0.2)Ga_(0.8))₂O₃/(Al_(0.4)Ga_(0.6))₂O₃.

Also shown are ohmic contact metals 1260 and 1280. The conduction bandedge E_(C)(z) 1265 and the valence band edges E_(V)(z) 1270 and the MQWregion 1400 shows the modulation in bandgap energy with respect to thespatially modulated composition. This is yet another particularadvantage of atomic layer epitaxy deposition techniques which make suchstructures possible.

FIG. 47 shows schematically the confined electron 1285 and hole 1290wavefunctions within the MQW region 1275. The electric-dipole transitiondue to spatial recombination of electron 1285 and hole 1290 createsphoton 1295.

The emission spectrum can be calculated and is shown in FIG. 48, plottedin graph 1300 as the emission wavelength 1310 and the oscillatorabsorption strength 1305 due to the wavefunction overlap integrals forthe spatially dependent quantized electron and holes states (alsoindicative of the emission strength). A plurality of peaks 1320, 1325and 1330 are generated due to recombination of quantized energy stateswith the MQW. In particular, the lowest energy electron-holerecombination peak 1320 is the most probable and occurs at ˜245 nm.Region 1315 shows that below the energy gap of the MQW there is noabsorption or optical emission. The first onset of optical activity inmoving toward shorter wavelengths is the n=1 exciton peak 1320determined by the MQW configuration.

The MQW configurations 1275, 1360, 1400 and 1460 result in lightemission energy peaks 1320 (FIG. 48), 1370 (FIG. 50), 1420 (FIG. 52) and1470 (FIG. 54) having peak operating wavelengths of 245 nm, 237 nm, 230nm and 215 nm, respectively. Graph 1365 of FIG. 50 also shows peaks 1375and 1380 along with region 1385. Graph 1410 of FIG. 52 also shows peaks1425 and 1430 along with region 1435. Graph 1465 of FIG. 54 also showspeak 1475 along with region 1480. Regions 1385, 1435 and 1480 show thatthere is no optical absorption or emission for photon energy/wavelengthsbelow the energy gap of the MQW.

Yet a further feature of extremely wide bandgap metal oxidesemiconductors is the configuration of ohmic contacts to n-type andp-type regions. The example diode structures 1255 comprise highwork-function metal 1280 and low work-function metal 1260 (ohmic contactmetals). This is because of the relative electron affinity of themetal-oxides with respect to vacuum (refer to FIG. 9).

FIGS. 48, 50, 52 and 54 show the optical absorption spectrum for the MQWregions contained within the diode structures 1255. The MQW comprisestwo layers of a narrower bandgap material and a wider bandgap material.The thickness of the layers, and in particular the narrow bandgap layer,are selected such that they are small enough to exhibit quantizationeffects along the growth direction within the conduction and valencepotentials wells that are formed. The absorption spectrum represents thecreation of an electron and hole in the quantized state of the MQW uponresonant absorption of an incident photon.

The reversible process of photon creation is where the electron and holeare spatially localized in their respective quantum energy levels of theMQW and recombine by virtue of the direct bandgap. The recombinationproducing a photon equals approximately to the layer acting as thepotential well having a direct energy gap in addition to the energyseparation of the quantized levels within the potentials wells relativeto the conduction and valence band edges. The emission/absorptionspectra therefore show the lowest lying energy resonance peak indicativeof the UVLED primary emission wavelength and is engineered to be thedesired operating wavelength of the device.

FIG. 55 shows a plot 1500 of the known pure metal work-function energy1510 and sorts the metal species (elemental metal contact 1505) fromhigh 1525 to low 1515 work function for application to p-type and n-typeohmic contacts and provides selection criteria for the metal contactsfor each of the conductivity type regions required by the UVLED. Line1520 represents the mid-point work function energy with respect to thehigh 1525 and low 1515 limits depicted in FIG. 55.

In some embodiments, Os, Pt, Ir, and Ni are used for the p-type regions,and low work-function metals selected from rare-earths, Li and Cs can beused. Other selections are also possible.

Intermediary contact materials such as semi-metallic palladium oxidePdO, degenerately doped Si or Ge and rare-earth nitrides can be used. Insome embodiments, ohmic contacts are formed in-situ to the depositionprocess for at least a portion of the contact materials to preserve the[metal contact/metal oxide] interface quality. In fact, single crystalmetal deposition is possible for some metal oxide configurations.

X-ray diffraction (XRD) is one of the most powerful tools available tocrystal growth analysis to directly ascertain crystallographic qualityand crystal symmetry type. FIGS. 56 and 57 show the two-dimensional XRDdata of example materials of ternary AlGaO₃ and a binary Al₂O₃/Ga₂O₃superlattice. Both structures are deposited pseudomorphically oncorundum crystal symmetry substrates having an A-plane oriented surface.

Referring now to FIG. 56, there is shown a reciprocal lattice map 2-axisx-ray diffraction pattern 1600 for a 201 nm thick epitaxial ternary(Al_(0.5)Ga_(0.5))₂O₃ on an A-plane Al₂O₃ substrate. Clearly, thein-plane and perpendicular mismatch of the ternary film is well matchedto the underlying substrate. The in-plane mismatch parallel to the planeof growth is ˜4088 ppm, and the perpendicular lattice mismatch of thefilm is ˜23440 ppm. The relatively vertical displacement of the ternarylayer peak (Al_(x)Ga_(1−x))₂O₃ with respect to the substrate (SUB) showsexcellent film growth compatibility and is directly advantageous forUVLED application.

Referring now to FIG. 57, there is shown a 2-axis x-ray diffractionpattern 1700 of a 10 period SL[Al₂O₃/Ga₂O₃] on an A-plane Al₂O₃substrate showing excellent strained Ga₂O₃ layers (no spread in 2thetaangle)=>elastically strained SL. The SL period=18.5 nm and an effectiveSL digital Al % ternary alloy, x_Al˜18%.

In further illustrative embodiments, an optoelectronic semiconductordevice in accordance with the present disclosure may be implemented asan ultraviolet laser device (UVLAS) based upon metal oxidesemiconducting materials.

The metal oxide compositions having bandgap energy commensurate withoperation in the UVC (150-280 nm) and far/vacuum UV wavelengths (120-200nm) have the general distinguishing feature of having intrinsicallysmall optical refractive index far from the fundamental band edgeabsorption. For operation as optoelectronic devices with energy statesin the immediate vicinity of the conduction and valence band edges theeffective refractive index is governed by the Krammers-Kronig relations.

FIGS. 58A-58B show a section of a metal-oxide semiconductor material1820 having optical length 1850 along a one-dimensional optical axis inaccordance with an illustrative embodiment of the present disclosure. Anincident light vector 1805 enters the material 1820 from air havingrefractive index n_(MOx). The light within the material 1820 istransmitted and reflected (beams 1810) at the refractive indexdiscontinuities at each surface with a transmitted optical beam 1815.

The material slab of length 1850 can support a number of opticallongitudinal modes 1825 as shown in FIG. 58A. The transmission 1815 as afunction of the optical wavelength incident upon the slab shows aFabry-Perot mode structure having modes 1825. For a photon trappedwithin the optical cavity defined by the one-dimensional slab it ispossible in accordance with the present disclosure to determine theroundtrip losses of the slab and the required minimum optical gainrequired to overcome these losses and enable a net gain.

The threshold gain is calculated in FIG. 58B showing the transmissionfactor β as a function of optical gain within the slab for the forward1830 and reverse 1835 propagating light beams 1810. For this simpleFabry-Perot case the low refractive index n_(MOx)=2.5 of slab lengthL_(cav)=1 micrometer requires a threshold gain 1845 calculated by thefull-width-half max point of the peak gain at 1840.

Some embodiments implement semiconductor cavities contained with avertical-type structure 110 (e.g., see FIG. 2A) with sub-micron lengthscales. This is because of the desire to localize the electron and holerecombination into a narrow region. Confining the physical thickness ofthe slab, where the carrier recombination occurs and light emission isgenerated, aids in reducing the threshold current density required toachieve lasing. It is therefore instructive to understand the requiredthreshold gain by reducing the gain slab length.

FIGS. 59A-59B show the same optical material as FIGS. 58A-58B, but forthe case of L_(cav)=500 nm. The smaller cavity length 1860 compared tolength 1850 results in fewer allowed optical modes 1870. The requiredthreshold gain required to overcome cavity losses is increased to 1865compared to the gain 1845 of FIG. 58A, referring to the peaks 1877calculated for forward and reverse propagating modes 1880 and 1885,respectively, shown in FIG. 59B.

The increase in required threshold gain for a slab of metal oxidematerial can be reduced dramatically by increasing the slab length ofthe optical gain medium—in this case the metal-oxide semiconductingregion responsible for the optical emission process.

Referring again to FIGS. 2A and 2B, instead of using vertical type 110emission devices (i.e., FIG. 2A), some embodiments utilize planarwaveguide structures where the optical mode overlaps an optical gainlayer along the plane parallel length. That is, even though the gainmaterial is still a thin slab the optical propagation vector issubstantially parallel to the plane of the gain slab.

This is shown schematically for structure 140 FIG. 2B and structure 2360in FIG. 74. Waveguide structures having optical gain region layerthicknesses well below 500 nm are possible and can even be as thin as 1nanometer supporting a quantum well (refer to FIGS. 64 to 68). Thelongitudinal length of the waveguide can then be of the order of severalmicrons to even a few millimeters or even a centimeter. This is anadvantage of the waveguide structure. An added requirement is theability to confine and guide optical modes along the major axis lengthof the waveguide, which can be achieved by use of suitable refractiveindex discontinuities. Optical modes prefer to be guided in a higherrefractive index medium compared to the surrounding non-absorptivecladding regions. This can be achieved using metal-oxide compositions asset out in the present disclosure which can be preselected to exhibitadvantageous E-k band structure.

A UVLAS requires, in the most fundamental configuration, at least oneoptical gain medium and an optical cavity for recycling generatedphotons. The optical cavity must also present a high reflector (HR) withlow loss and an output coupling reflector (OC) that can transmit aportion of the optical energy generated with in the gain medium. The HRand OC reflectors are in general plane parallel or enable focusing ofthe energy within the cavity into the gain medium.

FIG. 60 shows schematically an embodiment of an optical cavity having HR1900, gain medium 1905 substantially filling the cavity of length 1935,and an OC 1915 having physical thickness 1910. The standing waves 1925and 1930 show two distinct optical wavelength optical fields that arematched to the cavity length. The outcoupled light 1920 is due to the OCleaking a portion of the trapped energy within the cavity gain medium1905. In one example, Aluminum metal of low thickness <15 nm is utilizedin the far or vacuum UV wavelength regions and the transmission can betuned accurately by the Al-film thickness 1910. The lowest energystanding wave 1925 has a node (peak intensity of the optical field) atthe center node 1945 of the cavity. The 1^(st) harmonic (standing wave1930) exhibits to nodes 1940 and 1950, as shown.

FIG. 61 shows output wavelengths 1960 and 1965 from the cavity withenergy flow 1970. The cavity length 1935 is the same as in FIG. 60. FIG.61 shows that the cavity length 1935 can support two optical modesforming standing waves 1930 and 1925 of two different wavelengths. FIG.61 shows the emission or outcoupling of both wavelength modes (standingwaves 1930 and 1925) as wavelengths 1965 and 1960, respectively. Thatis, both modes propagate. Optical gain medium 1905 substantially fillsthe optical cavity length 1935. Only the peak optical field intensitynodes 1940, 1945 and 1950 couples to the spatial portions of the gainmedium 1905. It is therefore possible in accordance with the presentdisclosure to configure the gain medium within the optical cavity asshown in FIG. 62.

FIG. 62 shows a spatially selective gain medium 1980 which is contractedin length compared to optical gain medium 1905 of FIGS. 60-61 and ispositioned advantageously within cavity length 1935 to amplify only themode 1925. That is, optical gain medium 1980 favors the outcoupling ofwavelength 1960 as the optical mode. The cavity thus preferentiallyprovides gain to the fundamental mode 1925 with output energy selectedas wavelength 1960.

Similarly, FIG. 63 shows two spatially selective gain media 1990 and1995 positioned advantageously to amplify only the mode of standing wave1930. The cavity preferentially provides gain to the mode of standingwave 1930 with output energy selected as 1965.

This method involving spatially positioning the gain regions within theoptical cavity is one example embodiment of the present disclosure. Thiscan be achieved by predetermining the functional regions as a functionof the growth direction during film formation process as describedherein. A spacer layer between the gain sections can comprisesubstantially non-absorbing metal-oxide compositions and otherwiseprovide electronic carrier transport functions, and aid in the opticalcavity tuning design.

Attention is now directed towards the optical gain medium design forapplication to UVLAS using metal-oxide compositions set out in thepresent disclosure.

FIGS. 64A-64B and 65A-65B disclose bandgap engineered quantumconfinement structures of a single quantum well (QW). It is to beunderstood a plurality of QWs is possible, as is a superlattice. Thewide bandgap electronic barrier cladding layers are selected frommetal-oxide material composition A_(x)B_(y)O_(z) and the potential wellmaterial is selected as C_(p)D_(q)O_(r). Metal cations A, B, C and D areselected from the compositions set out in the present disclosure (0≤x,y, z, p, q, r≤1).

Predetermined selection of materials can achieve the conduction andvalence band offsets as shown in FIGS. 64A and 64B. The case of A=Al,B=Ga to form (Al_(0.95)B_(0.05))₂O₃═Al_(1.9)Ga_(0.1)O₃ and C=Al, D=Ga toform (Al_(0.05)B_(0.95))₂O₃═Al_(0.1)Ga_(1.9)O₃ is shown. The conduction2005 and valence 2010 band spatial profile along a growth direction, zis shown using the k=0 representation of the respective E-k curves foreach material.

FIG. 64A shows the QW having thickness 2015 of L_(QW)=5 nm generatingquantized energy states 2025 and 2035 for the allowed states of theelectrons and holes in the conduction and valence bands, respectively.The lowest lying quantized electron state 2020 and highest quantizedvalence state 2030 participate in the spatial recombination process tocreate a photon of energy equal to 2040.

Similarly, FIG. 64B shows the QW having thickness 2050 of L_(QW)=2 nmgenerating quantized energy states within the potential well for theallowed states of the electrons and holes in the conduction and valencebands, respectively. The lowest lying quantized electron state 2055 andhighest quantized valence state 2060 participate in the spatialrecombination process to create a photon of energy equal to 2065.

Reducing the QW thickness yet further results in the spatial bandstructures of FIGS. 65A and 65B. FIG. 65A shows the QW having thickness2070 of L_(QW)=1.5 nm generating quantized energy states within thepotential well for the allowed states of the electrons and holes in theconduction 2005 and valence 2010 bands, respectively. The lowest lyingquantized electron state 2075 and highest quantized valence state 2080participate in the spatial recombination process to create a photon ofenergy equal to 2085.

FIG. 65B shows the QW having thickness 2090 of L_(QW)=1.0 nm generatingquantized energy states within the potential well for the allowed statesof the electrons and holes in the conduction and valence bands,respectively. The QW can only support a single quantized electron state2095 which participates with the highest quantized valence state 2100 inthe spatial recombination process to create a photon of energy equal to2105.

The spontaneous emission due to the spatial recombination of thequantized electron and hole states for the QW structures of FIGS. 64A,64B, 65A and 65B are shown in FIG. 66. The annihilation of the electronand hole pair creates energetic photons of wavelengths peaked at 2115,2120, 2125, 2130 and 2135 for the cases of L_(QW)=5.0, 2.5, 2.0, 1.5 and1 nm, respectively. Evident from the emission spectra of 2110 is theexcellent tunability of the operating wavelength possible for the gainmedium by virtue of using the same barrier and well compositions butcontrolling L_(QW).

Having fully described the utility of configuring metal-oxidecompositions for direct application to UVLAS gain media, refer now toFIGS. 67A and 67B which describe in further detail the electronicconfiguration of the gain medium. FIG. 67A shows again a QW configuredusing metal-oxide layers to form an example QW structure as describedpreviously.

The QW thickness 2160 is tuned to achieve recombination energy 2145. Thek=0 representation of the QW in FIG. 67A is representative of thenon-zero crystal wave vector dispersion of the quantized energy states2165 and 2180 for the electron (conduction band 2190) and hole (valenceband 2205) states. For completeness, the underlying bulk E-k dispersionare also shown as 2170 and 2175 at k=0 and 2185 and 2200 for non-zero k.The schematic E-k diagram is critical for describing the populationinversion mechanism for creating excess electrons and holes in theconduction and valence band necessary for providing optical gain.

The band structure shown in FIG. 68A describes the electronic energyconfiguration states when the conduction band quasi-Fermi energy level2230 is positioned such that it is above the electronic quantized energystate 2235. Similarly, the valence band quasi-Fermi energy is selectedto penetrate the valence band level 2245 creating an excess hole density2225. The E-k curve of conduction band 2195 shows that electron states2220 are filled with electrons having non-zero crystal momentum states|k|>0 being possible. Valence band level 2240 is the valence band edgeof the bulk material used in the narrow bandgap region of the MQW. Whenthe narrow bandgap material is confined in the MQW, the energy statesare quantized, creating the band structure dispersion for conductionband 2195 and valence band 2205. Valence band level 2240 is then thevalence band maximum of the MQW region. Valence band level 2245represents the Fermi energy level of the valence band when configured asa p-type material. This makes excess hole density 2225 region filledwith holes that can participate in optical gain.

Optical recombination process can occur for ‘vertical transitions’wherein the change in crystal momentum between the electron and holesstate is identically zero. The allowed vertical transitions are shown as2210 at k=0 and 2215 k≠0. Calculation of the integrated gain spectrumfor the representative band structure of FIG. 68A is shown in FIG. 68B.Specific input parameters for the gain spectra are L_(QW)=2 nm, anelectron to hole concentration ratio of 1.0, a carrier relaxation timeof τ=1 ns and an operating temperature of T=300 K. Curves 2275 to 2280show an increase in the electron concentration N_(e) where0≤N_(e)≤5×10²⁴ m⁻³.

Net positive gain 2250 is achievable under high electron concentrationswith threshold N_(e)˜4×10²⁴ m⁻³. These parameters are of the orderachievable by other technologically mature semiconductors such as GaAsand GaN. In some embodiments, the metal oxide semiconductor by virtue ofhaving an intrinsically high bandgap will also be less susceptible togain reduction with operating temperature. This is evidenced byconventional optically pumped high power solid-state Ti-doped Al₂O₃laser crystals.

FIG. 68B shows the net gain 2265 and net absorption 2270 as a functionof Ne. The range of crystal wave vectors which can contribute tovertical transitions determines the width of the net gain region 2250.This is fundamentally determined by the achievable excess electron 2220and hole 2225 states possible by manipulating the quasi-Fermi energies.

The region 2255 is below the fundamental bandgaps of the host QW and istherefore non absorbing. Optical modulators are therefore also possibleusing metal-oxide semiconductor QWs. Of note is the point of inducedtransparency 2260 where the QW achieves zero loss.

Manipulating the quasi-Fermi energy is not the only method available forcreating excess electron and hole pairs in the vicinity of thezone-center band structure enabling optical emission. Consider FIGS. 69Aand 69B showing the E-k band structures for the case of direct bandgapmaterials (FIG. 69A) and pseudo-direct bandgap materials, for example,metal-oxide SL with period selected to create valence maxima as shown incurves 2241 with hole states 2246 of FIG. 69B.

Assuming similar conduction band dispersions 2195, for both valence bandtypes of 2205 and 2241, a configuration can be achieved wherein the samevertical transitions are possible. Substantially similar gain spectra asdisclosed in FIG. 68B are possible for both types shown in FIGS. 69A and69B.

Yet a further method is disclosed for an alternative method of creatingelectron and hole states suitable for creating optical emission andoptical gain with metal-oxide semiconductor structures.

Consider FIGS. 70A and 70B, which show an impact ionization process witha metal-oxide semiconductor having a direct bandgap. While impactionization is a known phenomenon and process in semiconductors, not sowell known is the advantageous properties of extremely wide energybandgap metal oxides. One of the most promising properties that has beenfound in accordance with the present disclosure is the exceedingly highdielectric breakdown strength of metal-oxides.

In prior art small bandgap semiconductors such as Si, GaAs and the like,impact ionization processes when leveraged in device functions tend towear-out the materials by the creation of crystallographicdefects/damage. This degrades the material over time and limits thenumber of breakdown events possible before catastrophic device failure.

Extreme wide bandgap gap metal oxides with Eg>5 eV possess advantageousproperties for creating impact ionization light emission devices.

FIG. 70A shows a metal oxide direct bandgap of 2266 with a ‘hot’ (highenergy) electron injected into the conduction band at electron state2251 with excess kinetic energy 2261 with respect to the conduction band2256 edge. Metal-oxides can easily withstand excessively high electricalfields placed across thin films (V_(br)>1 to 10 MV/cm).

Operating with a metal oxide slab biased at below and close to thebreakdown voltage enables an impact ionization event as shown in FIG.70B. The energetic electron 2251 interacts with the crystal symmetry ofthe host and can produce a lower energy state by coupling to theavailable thermalizing with lattice vibration quanta called phonons andpair production. That is, the impact ionization event comprising a hotelectron 2251 is converted into two lower energy electron states 2276and 2281 near the conduction band minimum as well as a new hole state2286 created at the top of the valence band 2271. The electron-hole pairproduced 2291 is a potential recombination pair to create a photon ofenergy 2266.

It has been found in accordance with the present disclosure that impactionization pair production is possible for excess electron energy 2261of about half the bandgap energy 2266. For example, if E_(G)=5 eV 2266then hot electrons with respect to the conduction band edge of ˜2.5 eVcan initiate pair production process as described. This is achievablefor Al₂O₃/Ga₂O₃ heterostructures wherein an electron from Al₂O₃ isinjected into the Ga₂O₃ across the heterojunction. Impact ionization isa stochastic process and requires a minimum interaction length to createa finite energy distribution of electron-hole pairs. In general, 100 nmto 1 micron of interaction length is useful for creating significantpair production.

FIGS. 71A and 71B show that impact ionization is also possible inpseudo-direct and indirect band structure metal oxides. FIG. 71A recitesthe case previously for direct bandgap, and FIG. 71B shows the sameprocess for an indirect bandgap valence band 2294 wherein theelectron-hole pair production 2292 requires a k≠0 hole state 2296 to becreated, necessitating a phonon for momentum conservation. As such, FIG.71B demonstrates that an optical gain medium is also possible inpseudo-direct band structures such as 2294.

FIGS. 72A and 72B disclose further detail of the disclosure using impactionization processes for optical gain medium by selecting advantageousproperties of the band structure.

FIG. 72A describes the band structure of FIGS. 68A-68B, 69A-69B, 70A-70Band 71A-71B for in-plane crystal wave vectors k_(∥) and the wavevectoralong the quantization axis k_(Z) that is parallel to the epilayergrowth direction z.

The conduction 2320 and valence 2329 band dispersions are shown alongk_(Z) in FIG. 72A. If the k=0 spatial band structure of material havingbandgap 2266 depicted in FIG. 72A is plotted along the growth direction,the resulting spatial-energy band diagram is shown in FIG. 72B. Alongthe growth direction z, the hot electron 2251 a is injected into theconduction band producing impact ionization process and pair production2290. If a slab of the metal-oxide material is subjected to a largeelectric field directed along z, the band structure has a potentialenergy along z that is linearly decreasing. An impact ionization eventproducing electron 2276 and hole 2286 pair quasi-particle production2290 can undergo recombination and produce a bandgap energy photon.

The remaining electron 2276 can be accelerated by the applied electricfield to create another hot electron 2252. The hot electron 2252 canthen impact ionize and repeat the process. Therefore, the energysupplied by the external electric field can generate the pair productand photon generation process. This process is particularly advantageousfor metal-oxide light emission and optical gain formation.

Lastly, there are three laser topologies that can be utilizedadvantageously in accordance with the principles set out in the presentdisclosure.

The basic components are: (i) an electronic region forming andgenerating an optical gain region; and (ii) an optical cavity containingthe optical gain region.

FIG. 73 shows a semiconductor optoelectronic device in the form of avertical emission type UVLAS 2300 comprising an optical gain region 2330of thickness 2331; an electron injector 2310 region 2325; a holeinjector 2315 region 2335. Regions 2325 and 2335 may be n-type andp-type metal oxide semiconductors and substantially transparent to theoperating wavelength emitted from the device along axis 2305. Theelectrical excitation source 200 is operably connected to the device viaconductive layers 2340 and 2320 which are also operable as a highreflector and output coupler, respectively. The optical cavity betweenthe reflectors (conductive layers 2340 and 2320) is formed by the sum ofthe stack of layers 2325, 2330 and 2335.

A portion of the thickness of the reflectors is also included as thecavity thickness if they are partially absorbing and of multilayerdielectric type. For the case of pure and ideal metal reflectors, themirror thickness can be neglected. Therefore, the optical cavitythickness is governed by the layers 2325, 2330 and 2335, of which theoptical gain region 2330 is advantageously positioned with respect tothe cavity modes as described in FIGS. 61, 62 and 63. The photonrecycling 2350 is shown by the optical reflection from themirrors/reflectors 2340 and 2320.

Yet another option for creating a UVLAS structure as shown in FIG. 73 isan embodiment in which the reflectors 2320 and 2340 form part of theelectrical circuit and therefore must be conducting and must also beoperable as reflectors forming the optical cavity. This can be achievedby using elemental Aluminum layers to act as at least one of the HR orOC.

An alternative UVLAS configuration decouples the optical cavity from theelectrical portion for the structure. For example, FIG. 74 discloses aUVLAS 2360 having an optical cavity formed comprising HR 2340 and OC2320 that are not part of the electrical circuit. The optical gainregion 2330 is positioned with the cavity enabling photon recycling2350. The optical axis is directed along axis 2305. Insulating spacerlayer metal oxide regions may be provided within the cavity to tailorthe position of the gain region 2330 between the reflectors 2340 and2320. The electron 2325 and hole injectors and 2335 provide laterallytransported carriers into the gain region 2330.

Such as structure can be achieved for a vertical emitting UVLAS bycreating p-type and n-type regions laterally disposed to connect only aportion of the gain region. The reflectors may be positioned also on aportion of the optical gain region to create the cavity photon recycling2350.

Yet even a further illustrative embodiment is the waveguide device 2370shown in FIG. 75.

FIG. 75 shows the waveguide structure 2370 having a major axis 2305 withepitaxial regions formed sequentially along the growth direction zcomprising of electron injector 2325, optical gain region 2330 and holeinjector region 2335. Single-mode or multi-mode waveguide structureshaving refractive indices are selected to create confined opticalradiation of forward and reverse propagating modes 2375 and 2380. Thecavity length 2385 is terminated at each end with reflectors 2340 and2320. High reflector 2340 can be metallic or distributed feedback typecomprising etched grating or multilayer dielectric conformally coated toa ridge. The OC 2320 can be a metallic semi-transparent film ofdielectric coating or even a cleaved facet of the semiconductor slab.

As would be appreciated, optical gain regions may be formed usingmetal-oxide semiconductors in accordance with the present disclosurethat are electrically stimulated and/or optically pumped/stimulatedwhere the optical cavity may be formed in both vertical and waveguidestructures as required.

The present disclosure teaches new materials and processes for realizingoptoelectronic light emitting devices based on metal oxides capable ofgenerating light deep into the UVC and far/vacuum UV wavelength bands.These processes include tuning or configuring the band structure ofdifferent regions of the device using a number of different methodsincluding, but not limited to, composition selection to achieve desiredband structure including forming effective compositions by the use ofsuperlattices comprising different layers of repeating metal oxides. Thepresent disclosure also teaches the use of biaxial strain or uniaxialstrain to modify band structures of relevant regions of thesemiconductor device as well as strain matching between layers, e.g., ina superlattice, to reduce crystal defects during the formation of theoptoelectronic device.

As would be appreciated, metal oxide based materials are commonly knownin the prior-art for their insulating properties. Metal oxide singlecrystal compositions, such as Sapphire (corundum-Al₂O₃) are availablewith extremely high crystal quality and are readily grown in largediameter wafers using bulk crystal growth methods, such as Czochralski(CZ), Edge-fed growth (EFG) and Float-zone (FZ) growth. Semiconductinggallium-oxide having monoclinic crystal symmetry has been realized usingessentially the same growth methods as Sapphire. The melting point ofGa₂O₃ is lower than Sapphire so the energy required for the CZ, EFG andFZ methods is slightly lower and may help reduce the large scale costper wafer. Bulk alloys of AlGaO₃ bulk substrates have not yet beenattempted using CZ or EFG. As such, metal oxide layers of theoptoelectronic devices may be based on these metal oxide substrates inaccordance with examples of the present disclosure.

The two binary metal oxide materials Ga₂O₃ and Al₂O₃ exist in severaltechnologically relevant crystal symmetry forms. In particular, thealpha-phase (rhombohedral) and beta-phase (monoclinic) are possible forboth Al₂O₃ and Ga₂O₃. Ga₂O₃ energetically favors the monoclinicstructure whereas Al₂O₃ favors the rhombohedral for bulk crystal growth.In accordance with the present disclosure atomic beam epitaxy may beemployed using constituent high purity metals and atomic oxygen. Asdemonstrated in this disclosure, this enables many opportunities forflexible growth of heterogeneous crystal symmetry epitaxial films.

Two example classes of device structures that are particularly suitableto UVLED include: high Al-content Al_(x)Ga_(1−x)O₃ deposited on Al₂O₃substrates and high Ga-content AlGaO₃ on bulk Ga₂O₃ substrates. As hasbeen demonstrated in this disclosure, the use of digital alloys andsuperlattices further extends the possible designs for application toUVLEDs. As has also been demonstrated in some examples of the presentdisclosure, the selection of various Ga₂O₃ and Al₂O₃ surfaceorientations when presented for AlGaO₃ epitaxy can be used inconjunction with growth conditions such as temperature andmetal-to-atomic-oxygen ratio and relative metal ratio of Al to Ga inorder to predetermine the crystal symmetry type of the epitaxial filmswhich may be exploited to determine the band structure of the opticalemission or conductivity type regions

Throughout the specification and the claims that follow, unless thecontext requires otherwise, the words “comprise” and “include” andvariations such as “comprising” and “including” will be understood toimply the inclusion of a stated integer or group of integers, but notthe exclusion of any other integer or group of integers.

Unless otherwise defined, all terms used in the present disclosure,including technical and scientific terms, have the meaning as commonlyunderstood by one of ordinary skill in the art. By means of furtherguidance, term definitions are included to better appreciate theteaching of the present disclosure.

As used herein, the following terms have the following meanings:

“A”, “an”, and “the” as used herein refers to both singular and pluralreferents unless the context clearly dictates otherwise. By way ofexample, “a metal oxide” refers to one or more than one metal oxide.

“About” as used herein referring to a measurable value such as aparameter, an amount, a temporal duration, and the like, is meant toencompass variations of +/−20% or less, preferably +/−10% or less, morepreferably +/−5% or less, even more preferably +/−1% or less, and stillmore preferably +/−0.1% or less of and from the specified value, in sofar such variations are appropriate to perform in the disclosedembodiments. However, it is to be understood that the value to which themodifier “about” refers is itself also specifically disclosed.

The expression “% by weight” (weight percent), here and throughout thedescription unless otherwise defined, refers to the relative weight ofthe respective component based on the overall weight of the formulationor element referred to.

The recitation of numerical ranges by endpoints includes all numbers andfractions subsumed within that range, as well as the recited endpoints,except where otherwise explicitly stated by disclaimer and the like.

The reference to any prior art in this specification is not, and shouldnot be taken as, an acknowledgement of any form of suggestion that suchprior art forms part of the common general knowledge.

Reference has been made to embodiments of the disclosed invention. Eachexample has been provided by way of explanation of the presenttechnology, not as a limitation of the present technology. In fact,while the specification has been described in detail with respect tospecific embodiments of the invention, it will be appreciated that thoseskilled in the art, upon attaining an understanding of the foregoing,may readily conceive of alterations to, variations of, and equivalentsto these embodiments. For instance, features illustrated or described aspart of one embodiment may be used with another embodiment to yield astill further embodiment. Thus, it is intended that the present subjectmatter covers all such modifications and variations within the scope ofthe appended claims and their equivalents. These and other modificationsand variations to the present invention may be practiced by those ofordinary skill in the art, without departing from the scope of thepresent invention, which is more particularly set forth in the appendedclaims. Furthermore, those of ordinary skill in the art will appreciatethat the foregoing description is by way of example only, and is notintended to limit the invention.

What is claimed is:
 1. An optoelectronic semiconductor light emittingdevice comprising: a substrate; and a plurality of epitaxialsemiconductor layers disposed on the substrate, wherein a firstepitaxial semiconductor layer of the plurality of epitaxialsemiconductor layers comprises a first single crystal oxide materialcomprising: at least one of magnesium, nickel, and zinc; at least one ofaluminum and gallium; and oxygen, wherein the first single crystal oxidematerial comprises a cubic crystal symmetry, and wherein theoptoelectronic semiconductor light emitting device is configured to emitlight having a wavelength in a range from 150 nm to 425 nm.
 2. Theoptoelectronic semiconductor light emitting device of claim 1, whereinthe substrate has monoclinic, corundum, or hexagonal crystal symmetry.3. The optoelectronic semiconductor light emitting device of claim 1,wherein the first epitaxial semiconductor layer comprises an Fd-3m spacegroup.
 4. The optoelectronic semiconductor light emitting device ofclaim 1, wherein the first epitaxial semiconductor layer comprises(Mg_(x)Zn_(1−x))_(z)(Al_(y)Ga_(1−y))_(2(1−z))O_(3−2x) wherein 0≤x≤1,0≤y≤1, and 0≤z≤1.
 5. The optoelectronic semiconductor light emittingdevice of claim 1, wherein the first epitaxial semiconductor layercomprises (Ni_(x)Mg_(1−x))_(y)Ga_(2(1−y))O_(3−2y) wherein 0≤x≤1 and0≤y≤1.
 6. The optoelectronic semiconductor light emitting device ofclaim 1, wherein the first epitaxial semiconductor layer comprisesternary Mg_(x)Ga_(2(1−x))O_(3−2x) wherein 0<x<1.
 7. The optoelectronicsemiconductor light emitting device of claim 1, wherein the firstepitaxial semiconductor layer comprises ternaryNi_(x)Ga_(2(1−x))O_(3−2x) wherein 0<x<1.
 8. The optoelectronicsemiconductor light emitting device of claim 1, wherein the firstepitaxial semiconductor layer comprises ternaryZn_(x)Ga_(2(1−x))O_(3−2x) wherein 0<x<1.
 9. The optoelectronicsemiconductor light emitting device of claim 1, wherein the firstepitaxial semiconductor layer comprises ternaryMg_(x)Al_(2(1−x))O_(3−2x) wherein 0<x<1.
 10. The optoelectronicsemiconductor light emitting device of claim 1, wherein the firstepitaxial semiconductor layer comprises ternaryNi_(x)Al_(2(1−x))O_(3−2x) wherein 0<x<1.
 11. The optoelectronicsemiconductor light emitting device of claim 1, wherein the firstepitaxial semiconductor layer comprises ternary Al_(2x)Zn_(1−x)O_(2x+1)wherein 0<x<1.
 12. The optoelectronic semiconductor light emittingdevice of claim 1, further comprising a superlattice, wherein thesuperlattice comprises alternating layers of the first epitaxialsemiconductor layer and of a second epitaxial semiconductor layer,wherein the second epitaxial semiconductor layer comprises a secondsingle crystal oxide material.
 13. The optoelectronic semiconductorlight emitting device of claim 12, wherein the second epitaxial oxidelayer comprises Ga₂O₃.
 14. The optoelectronic semiconductor lightemitting device of claim 13, wherein the Ga₂O₃ has monoclinic crystalsymmetry.
 15. The optoelectronic semiconductor light emitting device ofclaim 12, wherein the second epitaxial oxide layer comprises Al₂O₃. 16.The optoelectronic semiconductor light emitting device of claim 15,wherein the Al₂O₃ has monoclinic crystal symmetry.
 17. Theoptoelectronic semiconductor light emitting device of claim 1, whereinthe substrate is Al₂O₃ or Ga₂O₃.
 18. The optoelectronic semiconductorlight emitting device of claim 1, wherein the substrate is selected fromMgO, MgAl₂O₄, and MgGa₂O₄.
 19. The optoelectronic semiconductor lightemitting device of claim 1, wherein the substrate is LiF or MgF₂. 20.The optoelectronic semiconductor light emitting device of claim 1,wherein the substrate is LiGaO₂ or LiAlO₂.
 21. The optoelectronicsemiconductor light emitting device of claim 1, wherein the substrate isLaAlO₃.
 22. The optoelectronic semiconductor light emitting device ofclaim 1, wherein the substrate is TiO₂ or quartz.
 23. The optoelectronicsemiconductor light emitting device of claim 1, wherein the substrate isSiC.
 24. The optoelectronic semiconductor light emitting device of claim1, wherein the first epitaxial semiconductor layer is in an activeregion of the optoelectronic semiconductor light emitting device.